Pesticidal mixtures including spiroheterocyclic pyrrolidine diones

ABSTRACT

A pesticidal mixture comprising as active ingredient a mixture of component A and component B, wherein component A is a compound of formula (I), in which Q is i or ii wherein X, Y and Z, m and n, A, G, and R, are as defined as in claim  1 , and component B is a compound selected from the insecticides as defined in claim  1 . The present invention also relates to methods of using said mixtures for the control of plant pests.

RELATED APPLICATION INFORMATION

This application is a 371 of International Application No.PCT/EP2013/050790, filed 17 Jan. 2013, which claims priority to EPPatent Application No. 12151401.2, filed 17 Jan. 2012, the contents ofwhich are incorporated herein by reference herein.

The present invention relates to mixtures of pesticidally activeingredients and to methods of using the mixtures to control insects,acarines, nematodes or molluscs.

WO 2009/049851, WO 2010/063670 and WO10/066780 disclose that certainspiroheterocyclic pyrrolidine diones have insecticidal activity.

The present invention provides pesticidal mixtures comprising as activeingredient a mixture of component A and component B, wherein component Ais a compound of formula (I)

in which Q isi or ii

X, Y and Z independently of each other are C₁₋₄alkyl, C₁₋₄haloalkyl,C₁₋₄ alkoxy, C₁₋₄ haloalkoxy, halogen;m and n, independently of each other, are 0, 1, 2 or 3 and m+n is 0, 1,2 or 3;G is hydrogen, a metal, an ammonium, a sulfonium or a latentiatinggroup;R is hydrogen, C₁₋₄alkyl, C₁₋₄haloalkyl;A is hydrogen, C₁₋₄alkyl, C₁₋₄haloalkyl, C₂₋₄alkenyl, C₂₋₄haloalkenyl,C₁₋₄alkoxy(C₁₋₄)alkyl, C₁₋₄haloalkoxy(C₁₋₄)alkyl,C₁₋₄alkoxy(C₁₋₄)alkoxy(C₁₋₄)alkyl, tetrahydrofuranyl, tetrahydropyranyl;andor an agrochemically acceptable salt or an N-oxide thereof;and component B is selected from at least one of:

-   -   a) Imidaclothiz

-   -   b) Thiacloprid    -   c) Acetamiprid    -   d) Imidacloprid    -   e) Nitenpyram    -   f) Dinotefuran    -   g) Clothianidin

In the compounds of formula (I) of Component A, each alkyl moiety eitheralone or as part of a larger group is a straight or branched chain andis, for example, methyl, ethyl, n-propyl, n-butyl, iso-propyl,sec-butyl, iso-butyl, and tert-butyl.

Alkoxy groups preferably have a preferred chain length of from 1 to 4carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy,iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy and tert-butoxy. Suchgroups can be part of a larger group such as alkoxyalkyl andalkoxyalkoxyalkyl. Alkoxyalkyl groups preferably have a chain length of1 to 4 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl,methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethylor iso-propoxymethyl.

Halogen is generally fluorine, chlorine, bromine or iodine. This alsoapplies, correspondingly, to halogen in combination with other meanings,such as haloalkyl or haloalkoxy.

Haloalkyl and haloalkoxy groups preferably have a chain length of from 1to 4 carbon atoms. Haloalkyl is, for example, fluoromethyl,difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl,trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl,pentafluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl,2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl; preferablytrichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyland dichlorofluoromethyl. Haloalkoxy is, for example, fluoromethoxy,difluoromethoxy, trifluoromethoxy, chloromethoxy, dichloromethoxy,trichloromethoxy, 2,2,2-trifluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy,pentafluoroethoxy, 1,1-difluoro-2,2,2-trichloroethoxy,2,2,3,3-tetrafluoroethoxy and 2,2,2-trichloroethoxy; preferablytrichloromethoxy, difluorochloromethoxy, difluoromethoxy,trifluoromethoxy and dichlorofluoromethoxy.

The latentiating groups G are selected to allow its removal by one or acombination of biochemical, chemical or physical processes to affordcompounds of formula (I) where G is hydrogen before, during or followingapplication to the treated area or plants. Examples of these processesinclude enzymatic cleavage, chemical hydrolysis and photoloysis.Compounds bearing such groups G may offer certain advantages, such asimproved penetration of the cuticula of the plants treated, increasedtolerance of crops, improved compatibility or stability in formulatedmixtures containing other herbicides, herbicide safeners, plant growthregulators, fungicides or insecticides, or reduced leaching in soils.

Such latentiating groups are known in the art, for example, fromWO08/071405, WO09/074314, WO09/049851, WO10/063670 and WO10/066780.

In one embodiment, the latentiating group G is selected from the group—C(═O)—R^(a) and —C(═O)—O—R^(b); wherein R^(a) is selected fromhydrogen, C₁-C₁₂alkyl, C₂-C₁₂alkenyl, C₂-C₁₂alkynyl, C₁-C₁₀haloalkyl andR^(b) is selected from C₁-C₁₂alkyl, C₂-C₁₂alkenyl, C₂-C₁₂alkynyl andC₁-C₁₀haloalkyl. In particular, R^(a) and R^(b) are selected from thegroup consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl,iso-butyl, sec-butyl, tert-butyl, ethenyl and propenyl, e.g.2-propen-1-yl.

It is preferred that G is hydrogen, a metal, preferably an alkali metalor alkaline earth metal, or an ammonium or sulfonium group, wherehydrogen is especially preferred.

Depending on the nature of the substituents, compounds of formula (I)may exist in different isomeric forms. When G is hydrogen, for example,compounds of formula (I) may exist in different tautomeric forms:

This invention covers all isomers and tautomers and mixtures thereof inall proportions. Also, when substituents contain double bonds, cis- andtrans-isomers can exist. These isomers, too, are within the scope of theclaimed compounds of the formula (I).

The invention relates also to the agriculturally acceptable salts whichthe compounds of formula (I) are able to form with transition metal,alkali metal and alkaline earth metal bases, amines, quaternary ammoniumbases or tertiary sulfonium bases.

Among the transition metal, alkali metal and alkaline earth metal saltformers, special mention should be made of the hydroxides of copper,iron, lithium, sodium, potassium, magnesium and calcium, and preferablythe hydroxides, bicarbonates and carbonates of sodium and potassium.

Examples of amines suitable for ammonium salt formation include ammoniaas well as primary, secondary and tertiary C₁-C₁₈alkylamines,C₁-C₄hydroxyalkylamines and C₂-C₄alkoxyalkyl-amines, for examplemethylamine, ethylamine, n-propylamine, i-propylamine, the fourbutylamine isomers, n-amylamine, i-amylamine, hexylamine, heptylamine,octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine,heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine,methylhexylamine, methylnonylamine, methylpentadecylamine,methyloctadecylamine, ethylbutylamine, ethylheptylamine,ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine,diethylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine,di-n-amylamine, di-i-amylamine, dihexylamine, diheptylamine,dioctylamine, ethanolamine, n-propanolamine, i-propanolamine,N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine,allylamine, n-but-2-enylamine, n-pent-2-enylamine,2,3-dimethylbut-2-enylamine, dibut-2-enylamine, n-hex-2-enylamine,propylenediamine, trimethylamine, triethylamine, tri-n-propylamine,tri-i-opropylamine, tri-n-butylamine, tri-i-butylamine,tri-sec-butylamine, tri-n-amylamine, methoxyethylamine andethoxyethylamine; heterocyclic amines, for example pyridine, quinoline,isoquinoline, morpholine, piperidine, pyrrolidine, indoline,quinuclidine and azepine; primary arylamines, for example anilines,methoxyanilines, ethoxyanilines, o-, m- and p-toluidines,phenylenediamines, benzidines, naphthylamines and o-, m- andp-chloroanilines; but especially triethylamine, i-propylamine anddi-i-propylamine.

Preferred quaternary ammonium bases suitable for salt formationcorrespond, for example, to the formula [N(R_(a)R_(b)R_(c)R_(d))]OH,wherein R_(a), R_(b), R_(c) and R_(d) are each independently of theothers hydrogen or C₁-C₄alkyl. Further suitable tetraalkylammonium baseswith other anions can be obtained, for example, by anion exchangereactions.

Preferred tertiary sulfonium bases suitable for salt formationcorrespond, for example, to the formula [SR_(e)R_(f)R_(g)]OH, whereinR_(e), R_(f) and R_(g) are each independently of the others C₁-C₄ alkyl.Trimethylsulfonium hydroxide is especially preferred. Suitable sulfoniumbases may be obtained from the reaction of thioethers, in particulardialkylsulfides, with alkylhalides, followed by conversion to a suitablebase, for example a hydroxide, by anion exchange reactions.

The compounds of the invention may be made by a variety of methods asdescribed in detail, for example, in WO09/049851, WO10/063670 andWO10/066780.

It should be understood that in those compounds of formula (I), where Gis a metal, ammonium or sulfonium as mentioned above and as suchrepresents a cation, the corresponding negative charge is largelydelocalised across the O—C═C—C═O unit.

The compounds of formula (I) according to the invention also includehydrates which may be formed during the salt formation.

Preferably, in the compounds of the formula (I), the substituent R ishydrogen, C₁₋₄alkyl, C₁₋₄haloalkyl, in particular methyl, ethyl,iso-propyl, n-propyl, tert-butyl, sec-butyl, iso-butyl, or n-butyl.

Preferably, X, Y and Z, are selected, independently of one another, fromC₁-C₄alkyl, C₁-C₄alkoxy or halogen, in particular methyl, ethyl,iso-propyl, n-propyl, methoxy, fluoro, bromo or chloro, when m+n is 1, 2or 3, in particular, when m+n is 1 or 2.

Alternatively, Y and Z, independently of each other, denote C₁-C₄alkyl,C₁-C₄alkoxy, halogen, in particular methyl, ethyl, iso-propyl, n-propyl,methoxy, fluoro, chloro, bromo, when m+n is 1, 2 or 3, in particular,when m+n is 1 or 2.

In a particular embodiment, in the compound of formula (I), when m is 1,Y is in an ortho position and X and Y are each selected independentlyfrom the group consisting of methyl, ethyl, iso-propyl and n-propyl.

In another embodiment, preferably combined with the previous embodiment,wherein when n is 1 in the compound of formula (I), Z is in the paraposition and is selected from the group consisting of fluoro, bromo andchloro, methyl, ethyl, iso-propyl and n-propyl. Preferably, Z is methyl,fluoro, bromo and chloro. More preferably, Z is chloro or methyl.

In another embodiment, wherein in the compound of formula (I), m and nare each 1, Y is in an ortho position and X and Y are selectedindependently from the group consisting of methyl and ethyl, and Z is inthe para position and is selected from the group consisting of fluoro,bromo and chloro. Preferably, X and Y are each in an ortho position andare methyl and preferably Z is in a para position and is chloro ormethyl.

In the compounds of the formula (I), the substituent A is preferablyhydrogen, C₁₋₄alkyl, C₁₋₄haloalkyl, C₂₋₄alkenyl, C₁₋₄alkoxy(C₁₋₄)alkyl,C₁₋₄alkoxy(C₁₋₄)alkoxy(C₁₋₄)alkyl, tetrahydrofuranyl, tetrahydropyranyl,in particular methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl,sec-butyl, and tert-butyl, trifluoromethyl, 2,2,2-trifluoroethyl,2,2-difluoroethyl, 2-fluoroethyl, allyl, methoxymethyl, ethoxymethyl,methoxyethyl, methoxypropyl, methoxyethoxymethyl, methoxymethoxyethyl,tetrahydrofuran-2-yl, tetrahydropyran-2-yl, tetrahydrofuran-3-yl,tetrahydropyran-4-yl.

In the compounds of the formula (I), Q is preferably (i).

In one embodiment, when Q is (i), A is preferably hydrogen.

In another embodiment, when Q is (i), A is selected from the groupconsisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl,sec-butyl, tert-butyl, methoxymethyl, ethoxymethyl and methoxyethyl.Preferably, when Q is (i), A is methyl.

In another embodiment, when Q is (ii), A is selected from the groupconsisting of hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl,iso-butyl, tert-butyl, methoxymethyl, ethoxymethyl, methoxyethyl,methoxypropyl, tetrahydrofuran-2-yl, tetrahydropyran-2-yl,tetrahydrofuran-3-yl and tetrahydropyran-4-yl. Preferably, when Q is(ii), A is hydrogen, methyl, ethyl, methoxymethyl, andtetrahydrofuran-2-yl.

In another preferred group of compounds of the formula (I), R is one ofhydrogen, methyl, ethyl or trifluoromethyl, X is methyl, ethyl ormethoxy, Y and Z, independently of each other, are methyl, ethyl,methoxy, fluoro, chloro or bromo, G is hydrogen or —(C═O)—O—CH2CH3 and Ahas the meanings assigned to it above.

In a particularly preferred group of compounds of the formula (I), R ismethyl or ethyl, X is methyl, ethyl, methoxy, fluoro, bromo or chloro, Yand Z, independently of each other, are methyl, ethyl, methoxy, fluoro,chloro, or bromo, G is hydrogen or —(C═O)—O—CH2CH3 and A has themeanings assigned to it above.

In a more preferred group of compounds of the formula (I), R is methylor ethyl, X is methyl, ethyl, methoxy, fluoro, bromo or chloro, Y and Z,independently of each other, are methyl, ethyl, methoxy, fluoro, chloro,bromo, G is hydrogen or —(C═O)—O—CH2CH3 and A is hydrogen, methyl,ethyl, isopropyl, trifluoromethyl, 2,2,2-trifluoroethyl,2,2-difluoroethyl, 2-fluoroethyl, tetrahydrofuran-2-ylmethyl,tetrahydropyran-2-ylmethyl, tetrahydrofuran-3-ylmethyl,tetrahydropyran-3-ylmethyl, tetrahydropyran-4-ylmethyl, allyl,methoxymethyl, ethoxymethyl, methoxyethyl, methoxypropyl,methoxyethoxymethyl, methoxymethoxyethyltetrahydrofuran-2-yl,tetrahydropyran-2-yl, tetrahydrofuran-3-yl, or tetrahydropyran-4-yl.

In a another preferred group of compounds of the formula (I), R ismethyl, X is methyl or methoxy, Y and Z, independently of each other,are methyl, ethyl, methoxy, chloro or bromo, G is hydrogen,methoxycarbonyl or propenyloxycarbonyl or —(C═O)—O—CH2CH3, and A ishydrogen, methyl, ethyl, methoxymethyl, tetrahydrofuran-2-yl ortetrahydrofuran-3-yl.

In a another preferred group of compounds of the formula (I), Q is (i),m is 1, n is 1, X is methyl, Y is in the ortho position and is methyl, Zis in the para position and is chloro, G is hydrogen or —(C═O)—O—CH2CH3,A is methyl, R is methyl.

In a another preferred group of compounds of the formula (I), Q is (i),m is 1, n is 1, X is methyl, Y is in the ortho position and is methyl, Zis in the para position and is chloro, G is hydrogen or —(C═O)—O—CH2CH3,A is hydrogen, R is methyl.

In a another preferred group of compounds of the formula (I), Q is (i),m is 1, n is 1, X is methyl, Y is in the ortho position and is methyl, Zis in the para position and is methyl, G is hydrogen or —(C═O)—O—CH2CH3,A is hydrogen, R is methyl.

The compounds of formula (I) according to the following Tables below canbe prepared according to the methods disclosed in the art mentionedabove.

TABLE 1 This table discloses the 107 compounds T1.001 to T1.107 of thesubformula (Ia): (Ia)

wherein R is CH₃, A is CH₃, G is —(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c)and R_(d) are as defined below: No. R_(a) R_(b) R_(c) R_(d) T1.001 Br HH H T1.002 Cl H H H T1.003 CH₃ H H H T1.004 CH₂CH₃ H H H T1.005 OCH₃ H HH T1.006 Br Cl H H T1.007 Cl Br H H T1.008 Cl Cl H H T1.009 Cl CH₃ H HT1.010 CH₃ Cl H H T1.011 CH₃ CH₃ H H T1.012 Cl H Cl H T1.013 Cl H CH₃ HT1.014 Cl H CH₂CH₃ H T1.015 Cl H OCH₃ H T1.016 CH₃ H CH₃ H T1.017 CH₃ HCH₂CH₃ H T1.018 CH₃ H OCH₃ H T1.019 CH₂CH₃ H CH₂CH₃ H T1.020 CH₂CH₃ HOCH₃ H T1.021 OCH₃ H OCH₃ H T1.022 Br H H Cl T1.023 Br H H CH₃ T1.024 ClH H Cl T1.025 Cl H H CH₃ T1.026 CH₃ H H Br T1.027 CH₃ H H Cl T1.028 CH₃H H CH₃ T1.029 CH₂CH₃ H H CH₃ T1.030 OCH₃ H H CH₃ T1.031 Cl H Cl BrT1.032 CH₃ H CH₃ Br T1.033 CH₃ H CH₃ Cl T1.034 Br Cl H CH₃ T1.035 Br CH₃H CH₃ T1.036 Cl Cl H Cl T1.037 Cl Br H CH₃ T1.038 Cl Cl H CH₃ T1.039 ClCH₃ H Cl T1.040 Cl CH₃ H CH₃ T1.041 CH₃ Br H CH₃ T1.042 CH₃ Cl H CH₃T1.043 CH₃ CH₃ H CH₃ T1.044 Br Br CH₃ H T1.045 Br Cl CH₃ H T1.046 Br CH₃Br H T1.047 Br CH₃ Cl H T1.048 Cl Br CH₃ H T1.049 Cl Cl Cl H T1.050 ClCl CH₃ H T1.051 Cl CH₃ Cl H T1.052 Cl CH₃ CH₂CH₃ H T1.053 Cl CH₃ OCH₃ HT1.054 CH₃ Br CH₃ H T1.055 CH₃ Cl CH₃ H T1.056 CH₃ CH₃ Br H T1.057 CH₃CH₃ Cl H T1.058 CH₃ CH₃ CH₃ H T1.059 CH₃ CH₃ CH₂CH₃ H T1.060 CH₃ CH₃OCH₃ H T1.061 CH₂CH₃ Br Br H T1.062 CH₂CH₃ Br Cl H T1.063 CH₂CH₃ Br CH₃H T1.064 CH₂CH₃ Br CH₂CH₃ H T1.065 CH₂CH₃ Br OCH₃ H T1.066 CH₂CH₃ Cl BrH T1.067 CH₂CH₃ Cl Cl H T1.068 CH₂CH₃ Cl CH₃ H T1.069 CH₂CH₃ Cl CH₂CH₃ HT1.070 CH₂CH₃ Cl OCH₃ H T1.071 CH₂CH₃ CH₃ Br H T1.072 CH₂CH₃ CH₃ Cl HT1.073 CH₂CH₃ CH₃ CH₂CH₃ H T1.074 CH₂CH₃ CH₃ OCH₃ H T1.075 CH₂CH₃ CH₂CH₃CH₃ H T1.076 CH₂CH₃ CH₂CH₃ CH₂CH₃ H T1.077 OCH₃ Br CH₃ H T1.078 OCH₃ ClCH₃ H T1.079 OCH₃ CH₃ Br H T1.080 OCH₃ CH₃ Cl H T1.081 OCH₃ CH₃ OCH₃ HT1.082 CH₃ CH₃ CH₃ F T1.083 CH₃ CH₃ CH₃ Cl T1.084 CH₃ CH₃ CH₃ Br T1.085CH₃ CH₃ CH₃ CH₃ T1.086 Cl CH₃ CH₃ CH₃ T1.087 CH₃ Cl CH₃ CH₃ T1.088 CH₃CH₃ Cl CH₃ T1.089 CH₂CH₃ CH₃ CH₃ CH₃ T1.090 OCH₃ CH₃ CH₃ CH₃ T1.091 CH₃F H Br T1.092 CH₃ CH₃ H Br T1.093 CH₂CH₃ CH₃ H CH₃ T1.094 OCH₃ CH₃ H CH₃T1.095 CH₂CH₃ Cl H CH₃ T1.096 OCH₃ Cl H CH₃ T1.097 Cl H CH₃ CH₃ T1.098CH₃ H CH₃ CH₃ T1.099 CH₂CH₃ H CH₃ CH₃ T1.100 OCH₃ H CH₃ CH₃ T1.101 F HCl CH₃ T1.102 Cl H F CH₃ T1.103 H CH₃ CH₃ CH₃ T1.104 Br CH₃ CH₃ CH₃T1.105 CH₃ H Cl CH₃ T1.106 CH₃ H Br CH₃ T1.107 Br H CH₃ CH₃

Table 2: This table discloses the 107 compounds T2.001 to T2.107 of theformula (Ia), wherein R is CH₃, A is CH₂CH₃, G is —(C═O)—O—CH2CH3 andR_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.

Table 3: This table discloses the 107 compounds T3.001 to T3.107 of theformula (Ia), wherein R is CH₃, A is n-C₃H₇, G is —(C═O)—O—CH2CH3 andR_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.

Table 4: This table discloses the 107 compounds T4.001 to T4.107 of theformula (Ia), wherein R is CH₃, A is i-C₃H₇, G is —(C═O)—O—CH2CH3 andR_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.

Table 5: This table discloses the 107 compounds T5.001 to T5.107 of theformula (Ia), wherein R is CH₃, A is n-C₄H₉, G is —(C═O)—O—CH2CH3 andR_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.

Table 6: This table discloses the 107 compounds T6.001 to T6.107 of theformula (Ia), wherein R is CH₃, A is i-C₄H₉, G is hydrogen and R_(a),R_(b), R_(c) and R_(d) are as defined in Table 1.

Table 7: This table discloses the 107 compounds T7.001 to T7.107 of theformula (Ia), wherein R is CH₃, A is t-C₄H₉, G is —(C═O)—O—CH2CH3 andR_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.

Table 8: This table discloses the 107 compounds T8.001 to T8.107 of theformula (Ia), wherein R is CH₃, A is 2,2-(CH₃)₂-propyl, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1.

Table 9: This table discloses the 107 compounds T9.001 to T9.107 of theformula (Ia), wherein R is CH₃, A is allyl, G is —(C═O)—O—CH2CH3 andR_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.

Table 1i0: This table discloses the 107 compounds T10.001 to T10.107 ofthe formula (Ia), wherein R is CH₃, A is CH₂—CH═C(CH₃)₂, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1.

Table 11: This table discloses the 107 compounds T11.001 to T11.107 ofthe formula (Ia), wherein R is CH₃, A is CH₂—CH═C(Cl)₂, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1.

Table 12: This table discloses the 107 compounds T12.001 to T12.107 ofthe formula (Ia), wherein R is CH₃, A is CH₂OCH₃, G is —(C═O)—O—CH2CH3and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.

Table 13: This table discloses the 107 compounds T13.001 to T13.107 ofthe formula (Ia), wherein R is CH₃, A is CH₂OCH₂CH₃, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1.

Table 14: This table discloses the 107 compounds T14.001 to T14.107 ofthe formula (Ia), wherein R is CH₃, A is CH₂CH₂OCH₃, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1.

Table 15: This table discloses the 107 compounds T15.001 to T15.107 ofthe formula (Ia), wherein R is CH₃, A is CH₂OCH₂CH₂OCH₃, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1.

Table 16: This table discloses the 107 compounds T16.001 to T16.107 ofthe formula (Ia), wherein R is CH₃, A is CH₂CH₂OCH₂OCH₃, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1.

Table 17: This table discloses the 107 compounds T17.001 to T17.107 ofthe formula (Ia), wherein R is CH₃, A is tetrahydrofuran-2-yl, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1.

Table 18: This table discloses the 107 compounds T18.001 to T18.107 ofthe formula (Ia), wherein R is CH₃, A is tetrahydrofuran-3-yl, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1.

Table 19: This table discloses the 107 compounds T19.001 to T19.107 ofthe formula (Ia), wherein R is CH₃, A is tetrahydropyran-2-yl, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1.

Table 20: This table discloses the 107 compounds T20.001 to T20.107 ofthe formula (Ia), wherein R is CH₃, A is tetrahydropyran-4-yl, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1.

Table 21: This table discloses the 107 compounds T21.001 to T21.107 ofthe formula (Ia), wherein R is CH₃, A is CH₂CH₂F, G is —(C═O)—O—CH2CH3and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.

Table 22: This table discloses the 107 compounds T22.001 to T22.107 ofthe formula (Ia), wherein R is CH₃, A is CH₂CHF₂, G is —(C═O)—O—CH2CH3and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.

Table 23: This table discloses the 107 compounds T23.001 to T23.107 ofthe formula (Ia), wherein R is CH₃, A is CH₂CF₃, G is hydrogen andR_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.

Table 24: This table discloses the 107 compounds T24.001 to T24.107 ofthe formula (Ia), wherein R is hydrogen, A is CH₃, G is —(C═O)—O—CH2CH3and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.

Table 25: This table discloses the 107 compounds T25.001 to T25.107 ofthe formula (Ia), wherein R is hydrogen, A is CH₂CH₃, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1.

Table 26: This table discloses the 107 compounds T26.001 to T26.107 ofthe formula (Ia), wherein R is hydrogen, A is i-C₃H₇, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1.

Table 27: This table discloses the 107 compounds T27.001 to T27.107 ofthe formula (Ia), wherein R is hydrogen, A is CH₂OCH₃, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1.

Table 28: This table discloses the 107 compounds T28.001 to T28.107 ofthe formula (Ia), wherein R is hydrogen, A is CH₂CH₂OCH₃, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1.

Table 29: This table discloses the 107 compounds T29.001 to T29.107 ofthe formula (Ia), wherein R is hydrogen, A is CH₂OCH₂CH₂OCH₃, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1.

Table 30: This table discloses the 107 compounds T30.001 to T30.107 ofthe formula (Ia), wherein R is hydrogen, A is CH₂CH₂OCH₂OCH₃, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1.

Table 31: This table discloses the 107 compounds T31.001 to T31.107 ofthe formula (Ia), wherein R is hydrogen, A is CH₂CHF₂, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1.

Table 32: This table discloses the 107 compounds T32.001 to T32.107 ofthe formula (Ia), wherein R is hydrogen, A is CH₂CF₃, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1.

Table 33: This table discloses the 107 compounds T33.001 to T33.107 ofthe formula (Ia), wherein R is CH₂CH₃, A is CH₃, G is —(C═O)—O—CH2CH3and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.

Table 34: This table discloses the 107 compounds T34.001 to T34.107 ofthe formula (Ia), wherein R is CH₂CH₃, A is CH₂CH₃, G is —(C═O)—O—CH2CH3and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.

Table 35: This table discloses the 107 compounds T35.001 to T35.107 ofthe formula (Ia), wherein R is CH₂CH₃, A is i-C₃H₇, G is —(C═O)—O—CH2CH3and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.

Table 36: This table discloses the 107 compounds T36.001 to T36.107 ofthe formula (Ia), wherein R is CH₂CH₃, A is CH₂OCH₃, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1.

Table 37: This table discloses the 107 compounds T37.001 to T37.107 ofthe formula (Ia), wherein R is CH₂CH₃, A is CH₂CH₂OCH₃, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1.

Table 38: This table discloses the 107 compounds T38.001 to T38.107 ofthe formula (Ia), wherein R is CH₂CH₃, A is CH₂OCH₂CH₂OCH₃, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1.

Table 39: This table discloses the 107 compounds T39.001 to T39.107 ofthe formula (Ia), wherein R is CH₂CH₃, A is CH₂CH₂OCH₂OCH₃, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1.

Table 40: This table discloses the 107 compounds T40.001 to T40.107 ofthe formula (Ia), wherein R is CH₂CH₃, A is CH₂CHF₂, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1.

Table 41: This table discloses the 107 compounds T41.001 to T41.107 ofthe formula (Ia), wherein R is CH₂CH₃, A is CH₂CF₃, G is —(C═O)—O—CH2CH3and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1.

Table 42: This table discloses the 107 compounds T42.001 to T42.107 ofthe formula (Ia), wherein R is CH₃, A is methoxypropyl, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1.

Table 43: This table discloses the 107 compounds T43.001 to T43.107 ofthe formula (Ia), wherein R is H, A is methoxypropyl, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1.

Table 44: This table discloses the 107 compounds T44.001 to T44.107 ofthe formula (Ia), wherein R is CH₂CH₃, A is methoxypropyl, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1.

TABLE 1ii This table discloses the 107 compounds T1ii.001 to T1ii.107 ofthe subformula (Ib): (Ib)

wherein R is CH₃, A is hydrogen, G is —(C═O)—O—CH2CH3 and R_(a), R_(b),R_(c) and R_(d) are as defined below: No. R_(a) R_(b) R_(c) R_(d)T1ii.001 Br H H H T1ii.002 Cl H H H T1ii.003 CH₃ H H H T1ii.004 CH₂CH₃ HH H T1ii.005 OCH₃ H H H T1ii.006 Br Cl H H T1ii.007 Cl Br H H T1ii.008Cl Cl H H T1ii.009 Cl CH₃ H H T1ii.010 CH₃ Cl H H T1ii.011 CH₃ CH₃ H HT1ii.012 Cl H Cl H T1ii.013 Cl H CH₃ H T1ii.014 Cl H CH₂CH₃ H T1ii.015Cl H OCH₃ H T1ii.016 CH₃ H CH₃ H T1ii.017 CH₃ H CH₂CH₃ H T1ii.018 CH₃ HOCH₃ H T1ii.019 CH₂CH₃ H CH₂CH₃ H T1ii.020 CH₂CH₃ H OCH₃ H T1ii.021 OCH₃H OCH₃ H T1ii.022 Br H H Cl T1ii.023 Br H H CH₃ T1ii.024 Cl H H ClT1ii.025 Cl H H CH₃ T1ii.026 CH₃ H H Br T1ii.027 CH₃ H H Cl T1ii.028 CH₃H H CH₃ T1ii.029 CH₂CH₃ H H CH₃ T1ii.030 OCH₃ H H CH₃ T1ii.031 Cl H ClBr T1ii.032 CH₃ H CH₃ Br T1ii.033 CH₃ H CH₃ Cl T1ii.034 Br Cl H CH₃T1ii.035 Br CH₃ H CH₃ T1ii.036 Cl Cl H Cl T1ii.037 Cl Br H CH₃ T1ii.038Cl Cl H CH₃ T1ii.039 Cl CH₃ H Cl T1ii.040 Cl CH₃ H CH₃ T1ii.041 CH₃ Br HCH₃ T1ii.042 CH₃ Cl H CH₃ T1ii.043 CH₃ CH₃ H CH₃ T1ii.044 Br Br CH₃ HT1ii.045 Br Cl CH₃ H T1ii.046 Br CH₃ Br H T1ii.047 Br CH₃ Cl H T1ii.048Cl Br CH₃ H T1ii.049 Cl Cl Cl H T1ii.050 Cl Cl CH₃ H T1ii.051 Cl CH₃ ClH T1ii.052 Cl CH₃ CH₂CH₃ H T1ii.053 Cl CH₃ OCH₃ H T1ii.054 CH₃ Br CH₃ HT1ii.055 CH₃ Cl CH₃ H T1ii.056 CH₃ CH₃ Br H T1ii.057 CH₃ CH₃ Cl HT1ii.058 CH₃ CH₃ CH₃ H T1ii.059 CH₃ CH₃ CH₂CH₃ H T1ii.060 CH₃ CH₃ OCH₃ HT1ii.061 CH₂CH₃ Br Br H T1ii.062 CH₂CH₃ Br Cl H T1ii.063 CH₂CH₃ Br CH₃ HT1ii.064 CH₂CH₃ Br CH₂CH₃ H T1ii.065 CH₂CH₃ Br OCH₃ H T1ii.066 CH₂CH₃ ClBr H T1ii.067 CH₂CH₃ Cl Cl H T1ii.068 CH₂CH₃ Cl CH₃ H T1ii.069 CH₂CH₃ ClCH₂CH₃ H T1ii.070 CH₂CH₃ Cl OCH₃ H T1ii.071 CH₂CH₃ CH₃ Br H T1ii.072CH₂CH₃ CH₃ Cl H T1ii.073 CH₂CH₃ CH₃ CH₂CH₃ H T1ii.074 CH₂CH₃ CH₃ OCH₃ HT1ii.075 CH₂CH₃ CH₂CH₃ CH₃ H T1ii.076 CH₂CH₃ CH₂CH₃ CH₂CH₃ H T1ii.077OCH₃ Br CH₃ H T1ii.078 OCH₃ Cl CH₃ H T1ii.079 OCH₃ CH₃ Br H T1ii.080OCH₃ CH₃ Cl H T1ii.081 OCH₃ CH₃ OCH₃ H T1ii.082 CH₃ CH₃ CH₃ F T1ii.083CH₃ CH₃ CH₃ Cl T1ii.084 CH₃ CH₃ CH₃ Br T1ii.085 CH₃ CH₃ CH₃ CH₃ T1ii.086Cl CH₃ CH₃ CH₃ T1ii.087 CH₃ Cl CH₃ CH₃ T1ii.088 CH₃ CH₃ Cl CH₃ T1ii.089CH₂CH₃ CH₃ CH₃ CH₃ T1ii.090 OCH₃ CH₃ CH₃ CH₃ T1ii.091 CH₃ F H BrT1ii.092 CH₃ CH₃ H Br T1ii.093 CH₂CH₃ CH₃ H CH₃ T1ii.094 OCH₃ CH₃ H CH₃T1ii.095 CH₂CH₃ Cl H CH₃ T1ii.096 OCH₃ Cl H CH₃ T1ii.097 Cl H CH₃ CH₃T1ii.098 CH₃ H CH₃ CH₃ T1ii.099 CH₂CH₃ H CH₃ CH₃ T1ii.100 OCH₃ H CH₃ CH₃T1ii.101 F H Cl CH₃ T1ii.102 Cl H F CH₃ T1ii.103 H CH₃ CH₃ CH₃ T1ii.104Br CH₃ CH₃ CH₃ T1ii.105 CH₃ H Cl CH₃ T1ii.106 CH₃ H Br CH₃ T1ii.107 Br HCH₃ CH₃

Table 2ii: This table discloses the 107 compounds T2ii.001 to T2ii.107of the formula (Ib), wherein R is CH₃, A is CH₃, G is —(C═O)—O—CH2CH3and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1ii.

Table 3ii: This table discloses the 107 compounds T3ii.001 to T3ii.107of the formula (Ib), wherein R is CH₃, A is CH₂CH₃, G is —(C═O)—O—CH2CH3and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1ii.

Table 4ii: This table discloses the 107 compounds T4ii.001 to T4ii.107of the formula (Ib), wherein R is CH₃, A is n-C₃H₇, G is —(C═O)—O—CH2CH3and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1ii.

Table 5ii: This table discloses the 107 compounds T5ii.001 to T5ii.107of the formula (Ib), wherein R is CH₃, A is i-C₃H₇, G is —(C═O)—O—CH2CH3and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1ii.

Table 6ii: This table discloses the 107 compounds T6ii.001 to T6ii.107of the formula (Ib), wherein R is CH₃, A is n-C₄H₉, G is —(C═O)—O—CH2CH3and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1ii.

Table 7ii: This table discloses the 107 compounds T7ii.001 to T7ii.107of the formula (Ib), wherein R is CH₃, A is i-C₄H₉, G is —(C═O)—O—CH2CH3and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1ii.

Table 8ii: This table discloses the 107 compounds T8ii.001 to T8ii.107of the formula (Ib), wherein R is CH₃, A is t-C₄H₉, G is —(C═O)—O—CH2CH3and R_(a), R_(b), R_(c) and R_(d) are as defined in Table 1ii.

Table 9ii: This table discloses the 107 compounds T9ii.001 to T9ii.107of the formula (Ib), wherein R is CH₃, A is 2,2-(CH₃)₂-propyl, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1ii.

Table 10ii: This table discloses the 107 compounds T10ii.001 toT10ii.107 of the formula (Ib), wherein R is CH₃, A is allyl, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1ii.

Table 11ii: This table discloses the 107 compounds T11ii.001 toT11ii.107 of the formula (Ib), wherein R is CH₃, A is CH₂—CH═C(CH₃)₂, Gis —(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1ii.

Table 12ii: This table discloses the 107 compounds T12ii.001 toT12ii.107 of the formula (Ib), wherein R is CH₃, A is CH₂—CH═C(Cl)₂, Gis —(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1ii.

Table 13ii: This table discloses the 107 compounds T13ii.001 toT13ii.107 of the formula (Ib), wherein R is CH₃, A is CH₂OCH₃, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1ii.

Table 14ii: This table discloses the 107 compounds T14ii.001 toT14ii.107 of the formula (Ib), wherein R is CH₃, A is CH₂OCH₂CH₃, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1ii.

Table 15ii: This table discloses the 107 compounds T15ii.001 toT15ii.107 of the formula (Ib), wherein R is CH₃, A is CH₂CH₂OCH₃, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1ii.

Table 16ii: This table discloses the 107 compounds T16ii.001 toT16ii.107 of the formula (Ib), wherein R is CH₃, A is CH₂OCH₂CH₂OCH₃, Gis —(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1ii.

Table 17ii: This table discloses the 107 compounds T17ii.001 toT17ii.107 of the formula (Ib), wherein R is CH₃, A istetrahydrofuran-2-yl, G is —(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) andR_(d) are as defined in Table 1ii.

Table 18ii: This table discloses the 107 compounds T18ii.001 toT18ii.107 of the formula (Ib), wherein R is CH₃, A istetrahydrofuran-3-yl, G is hydrogen and R_(a), R_(b), R_(c) and R_(d)are as defined in Table 1ii.

Table 19ii: This table discloses the 107 compounds T19ii.001 toT19ii.107 of the formula (Ib), wherein R is CH₃, A istetrahydropyran-2-yl, G is —(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) andR_(d) are as defined in Table 1ii.

Table 20ii: This table discloses the 107 compounds T20ii.001 toT20ii.107 of the formula (Ib), wherein R is CH₃, A istetrahydropyran-4-yl, G is —(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) andR_(d) are as defined in Table 1ii.

Table 21ii: This table discloses the 107 compounds T21ii.001 toT21ii.107 of the formula (Ib), wherein R is CH₃, A is CH₂CHF₂, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1ii.

Table 22ii: This table discloses the 107 compounds T22ii.001 toT22ii.107 of the formula (Ib), wherein R is hydrogen, A is hydrogen, Gis —(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1ii.

Table 23ii: This table discloses the 107 compounds T23ii.001 toT23ii.107 of the formula (Ib), wherein R is hydrogen, A is CH₃, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1ii.

Table 24ii: This table discloses the 107 compounds T24ii.001 toT24ii.107 of the formula (Ib), wherein R is hydrogen, A is CH₂OCH₃, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1ii.

Table 25ii: This table discloses the 107 compounds T25ii.001 toT25ii.107 of the formula (Ib), wherein R is hydrogen, A is CH₂CH₂OCH₃, Gis —(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1ii.

Table 26ii: This table discloses the 107 compounds T26ii.001 toT26ii.107 of the formula (Ib), wherein R is CH₂CH₃, A is hydrogen, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1ii.

Table 27ii: This table discloses the 107 compounds T27ii.001 toT27ii.107 of the formula (Ib), wherein R is CH₂CH₃, A is CH₃, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1ii.

Table 28ii: This table discloses the 107 compounds T28ii.001 toT28ii.107 of the formula (Ib), wherein R is CH₂CH₃, A is CH₂OCH₃, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1ii.

Table 29ii: This table discloses the 107 compounds T29ii.001 toT29ii.107 of the formula (Ib), wherein R is CH₂CH₃, A is CH₂CH₂OCH₃, Gis —(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1ii.

Table 30ii: This table discloses the 107 compounds T30ii.001 toT30ii.107 of the formula (Ib), wherein R is CH₃, A is CH₂CH₂CH₂OCH₃, Gis —(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1ii.

Table 31ii: This table discloses the 107 compounds T31ii.001 toT31ii.107 of the formula (Ib), wherein R is hydrogen, A is CH₂CH₃, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1ii.

Table 32ii: This table discloses the 107 compounds T32ii.001 toT32ii.107 of the formula (Ib), wherein R is hydrogen, A is allyl, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1ii.

Table 33ii: This table discloses the 107 compounds T33ii.001 toT33ii.107 of the formula (Ib), wherein R is hydrogen, A istetrahydrofuran-2-yl, G is —(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) andR_(d) are as defined in Table 1ii.

Table 34ii: This table discloses the 107 compounds T34ii.001 toT34ii.107 of the formula (Ib), wherein R is hydrogen, A istetrahydropyran-2-yl, G is —(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) andR_(d) are as defined in Table 1ii.

Table 35ii: This table discloses the 107 compounds T35ii.001 toT35ii.107 of the formula (Ib), wherein R is CH₂CH₃, A is CH₂CH₃, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1ii.

Table 36ii: This table discloses the 107 compounds T36ii.001 toT36ii.107 of the formula (Ib), wherein R is CH₂CH₃, A is allyl, G is—(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are as defined inTable 1ii.

Table 37ii: This table discloses the 107 compounds T37ii.001 toT37ii.107 of the formula (Ib), wherein R is CH₂CH₃, A istetrahydrofuran-2-yl, G is —(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) andR_(d) are as defined in Table 1ii.

Table 38ii: This table discloses the 107 compounds T38ii.001 toT38ii.107 of the formula (Ib), wherein R is CH₂CH₃, A istetrahydropyran-2-yl, G is —(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) andR_(d) are as defined in Table 1ii.

TABLE 1iii This table discloses the 87 compounds T1iii.001 to T1iii.87of the subformula (Ic): (Ic)

wherein R is CH₃, G is —(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d)are as defined below: No. R_(a) R_(b) R_(c) R_(d) T1iii.001 Br H H HT1iii.002 Cl H H H T1iii.003 CH₃ H H H T1iii.004 CH₂CH₃ H H H T1iii.005OCH₃ H H H T1iii.006 Br Cl H H T1iii.007 Cl Br H H T1iii.008 Cl Cl H HT1iii.009 Cl CH₃ H H T1iii.010 CH₃ Cl H H T1iii.011 CH₃ CH₃ H HT1iii.012 Cl H Cl H T1iii.013 Cl H CH₃ H T1iii.014 Cl H CH₂CH₃ HT1iii.015 Cl H OCH₃ H T1iii.016 CH₃ H CH₃ H T1iii.017 CH₃ H CH₂CH₃ HT1iii.018 CH₃ H OCH₃ H T1iii.019 CH₂CH₃ H CH₂CH₃ H T1iii.020 CH₂CH₃ HOCH₃ H T1iii.021 OCH₃ H OCH₃ H T1iii.022 Br H H Cl T1iii.023 Br H H CH₃T1iii.024 Cl H H Cl T1iii.025 Cl H H CH₃ T1iii.026 CH₃ H H Br T1iii.027CH₃ H H Cl T1iii.028 CH₃ H H CH₃ T1iii.029 CH₂CH₃ H H CH₃ T1iii.030 OCH₃H H CH₃ T1iii.031 Cl H Cl Br T1iii.032 CH₃ H CH₃ Br T1iii.033 CH₃ H CH₃Cl T1iii.034 Br Cl H CH₃ T1iii.035 Br CH₃ H CH₃ T1iii.036 Cl Cl H ClT1iii.037 Cl Br H CH₃ T1iii.038 Cl Cl H CH₃ T1iii.039 Cl CH₃ H ClT1iii.040 Cl CH₃ H CH₃ T1iii.041 CH₃ Br H CH₃ T1iii.042 CH₃ Cl H CH₃T1iii.043 CH₃ CH₃ H CH₃ T1iii.044 Br Br CH₃ H T1iii.045 Br Cl CH₃ HT1iii.046 Br CH₃ Br H T1iii.047 Br CH₃ Cl H T1iii.048 Cl Br CH₃ HT1iii.049 Cl Cl Cl H T1iii.050 Cl Cl CH₃ H T1iii.051 Cl CH₃ Cl HT1iii.052 Cl CH₃ CH₂CH₃ H T1iii.053 Cl CH₃ OCH₃ H T1iii.054 CH₃ Br CH₃ HT1iii.055 CH₃ Cl CH₃ H T1iii.056 CH₃ CH₃ Br H T1iii.057 CH₃ CH₃ Cl HT1iii.058 CH₃ CH₃ CH₃ H T1iii.059 CH₃ CH₃ CH₂CH₃ H T1iii.060 CH₃ CH₃OCH₃ H T1iii.061 CH₂CH₃ Br Br H T1iii.062 CH₂CH₃ Br Cl H T1iii.063CH₂CH₃ Br CH₃ H T1iii.064 CH₂CH₃ Br CH₂CH₃ H T1iii.065 CH₂CH₃ Br OCH₃ HT1iii.066 CH₂CH₃ Cl Br H T1iii.067 CH₂CH₃ Cl Cl H T1iii.068 CH₂CH₃ ClCH₃ H T1iii.069 CH₂CH₃ Cl CH₂CH₃ H T1iii.070 CH₂CH₃ Cl OCH₃ H T1iii.071CH₂CH₃ CH₃ Br H T1iii.072 CH₂CH₃ CH₃ Cl H T1iii.073 CH₂CH₃ CH₃ CH₂CH₃ HT1iii.074 CH₂CH₃ CH₃ OCH₃ H T1iii.075 CH₂CH₃ CH₂CH₃ CH₃ H T1iii.076CH₂CH₃ CH₂CH₃ CH₂CH₃ H T1iii.077 OCH₃ Br CH₃ H T1iii.078 OCH₃ Cl CH₃ HT1iii.079 OCH₃ CH₃ Br H T1iii.080 OCH₃ CH₃ Cl H T1iii.081 OCH₃ CH₃ OCH₃H T1iii.082 CH₃ CH₃ CH₃ F T1iii.083 CH₃ CH₃ CH₃ Cl T1iii.084 CH₃ CH₃ CH₃Br T1iii.085 CH₃ CH₃ CH₃ CH₃ T1iii.086 Cl CH₃ CH3 CH3 T1iii.087 CH3 ClCH3 CH3

Table 2iii: This table discloses the 87 compounds T2iii.001 to T2iii.87of the formula (Ic), wherein R is CH₂CH₃, R₁, R₂, R₃ and R₄ arehydrogen, G is —(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are asdefined in Table 1iii.

Table 3iii: This table discloses the 87 compounds T3iii.001 to T3iii.87of the formula (Ic), wherein R is n-C₃H₇, R₁, R₂, R₃ and R₄ arehydrogen, G is —(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are asdefined in Table 1iii.

Table 4iii: This table discloses the 87 compounds T4iii.001 to T4iii.87of the formula (Ic), wherein R is i-C₃H₇, R₁, R₂, R₃ and R₄ arehydrogen, G is —(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are asdefined in Table 1iii.

Table 5iii: This table discloses the 87 compounds T5iii.001 to T5iii.87of the formula (Ic), wherein R is hydrogen, R₁, R₂, R₃ and R₄ arehydrogen, G is —(C═O)—O—CH2CH3 and R_(a), R_(b), R_(c) and R_(d) are asdefined in Table 1iii.

The compounds of formula (I), including formula (Ia), (Ib) and (Ic), andtheir manufacturing processes, formulations and adjuvents are known fromWO 2009/049851, WO 2010/063670 and WO10/066780.

The present invention includes all isomers of compounds of formula (I),salts and N-oxides thereof, including enantiomers, diastereomers andtautomers. Component A may be a mixture of any type of isomer of acompound of formula (I), or may be substantially a single type ofisomer.

Any one of the above compounds from T1.001 to T44.107, T1ii.001 toT38ii.107 and T1iii. to T5iii.87 can be selected as component A to mixwith a component B selected from at least one of the following:

-   -   a) Imidaclothiz    -   b) Thiacloprid    -   c) Acetamiprid    -   d) Imidacloprid    -   e) Nitenpyram    -   f) Dinotefuran    -   g) Clothianidin

Preferably, component B is a compound selected from only one of a). tog). above. In other words, preferably the invention provides a twocomponent pesticidal mixture comprising as active ingredient a mixtureof component A of formula (I) (including any one of formula (Ia), (Ib)and (Ic)) and component B selected from one of a). to g).

Preferably, component B is one compound selected from the groupconsisting of:

-   -   a) Imidaclothiz    -   b) Thiacloprid    -   c) Acetamiprid    -   d) Imidacloprid    -   e) Nitenpyram    -   f) Dinotefuran    -   g) Clothianidin

Many sucking pests are known to be vectors of plant diseases caused bymicroorganisms like bacteria, viruses or phytoplasms. The combination ofthe compound according to formula (I) for component A and at least oneof these compounds for component B has the added advantage of aknock-down effect on various pests that may act as disease vectors, suchas for example whiteflies, scales, psyllids, aphids/plant lices andmites. With “knock-down effect”, it is meant that the pest to becontrolled is rapidly stopped from feeding, quickly totally immobilizedor even speedily killed (e.g. at least 80% mortality after 24 hours or80% mortality after 24 hours), thereby also reducing the risk ofinfection of the plant exposed to the specified diseases (e.g. viruses)spread by such pests. Preferably, the active ingredient is a mixture ofcomponent A as described above and component B selected from at leastone, preferably acetamiprid.

All of the components B from b) to g) are known, e.g. from “ThePesticide Manual”, Fifteenth Edition, Edited by Clive Tomlin, BritishCrop Protection Council. Reference to the above components B includesreference to their salts and any usual derivatives, such as esterderivatives and isomers.

Compound a) Imidaclothiz is a known compound with the IUPAC name(EZ)-1-(2-chloro-1,3-thiazol-5-ylmethyl)-N-nitroimidazolidin-2-ylideneamine:

It has now been found, surprisingly, that the active ingredient mixtureaccording to the invention not only delivers the additive enhancement ofthe spectrum of action with respect to the pest to be controlled butachieves a synergistic effect which can extend the range of action ofthe component A and of the component B in two ways. Firstly, the ratesof application of the component A and of the component B are loweredwhilst the action remains equally good. Secondly, the active ingredientmixture still achieves a high degree of pest control, sometimes evenwhere the two individual components have become totally ineffective insuch a low application rate range. This allows increased safety in use.

However, besides the actual synergistic action with respect to pestcontrol, the pesticidal compositions according to the invention can havefurther surprising advantageous properties which can also be described,in a wider sense, as synergistic activity. Examples of such advantageousproperties that may be mentioned are: a broadening of the spectrum ofpest control to other pests, for example to resistant strains; areduction in the rate of application of the active ingredients; adequatepest control with the aid of the compositions according to theinvention, even at a rate of application at which the individualcompounds are totally ineffective; advantageous behaviour duringformulation and/or upon application, for example upon grinding, sieving,emulsifying, dissolving or dispensing; increased storage stability;improved stability to light; more advantageuos degradability; improvedtoxicological and/or ecotoxicological behaviour; improvedcharacteristics of the useful plants including: emergence, crop yields,more developed root system, tillering increase, increase in plantheight, bigger leaf blade, less dead basal leaves, stronger tillers,greener leaf colour, less fertilizers needed, less seeds needed, moreproductive tillers, earlier flowering, early grain maturity, less plantverse (lodging), increased shoot growth, improved plant vigor, and earlygermination; or any other advantages familiar to a person skilled in theart.

The combinations according to the invention may also comprise more thanone of the active components B, if, for example, a broadening of thespectrum of pest control is desired. For instance, it may beadvantageous in the agricultural practice to combine two or threecomponents B with any of the compounds of formula (I), or with anypreferred member of the group of compounds of formula (I). The mixturesof the invention may also comprise other active ingredients in additionto components A and B.

In other preferred embodiments, the active ingredient is a mixture ofonly component A and a single active component as component B from thelist of a). to g). In other words the pesticidal composition haspreferably no more than two pesticidally active components.

Each substituent definition in each preferred group of compounds offormula (I) may be juxtaposed with any substituent definition in anyother preferred group of compounds, in any combination.

The weight ratio of A to B is preferably between 1000:1 and 1:100, morepreferably between 500:1 and 1:100. In other embodiments that weightratio of A to B may be between 250:1 to 1:66, for example between 125:1to 1:33, for example between 100:1 to 1:25, for example between 66:1 to1:10, for example between 33:1 to 1:5 etc. Such weight ratios lead tosynergistic mixtures.

The invention also provides pesticidal mixtures comprising a combinationof components A and B as mentioned above in a synergistically effectiveamount, together with an agriculturally acceptable carrier, andoptionally a surfactant.

The following mixtures are particularly favoured for treating plantsagainst pests such as Myzus persicae (Green peach aphid) and Tetranychusurticae (Two-spotted spider mite), which can be used in the weightratios mentioned above:

TABLE 45 Component A Component B Mixture 1 T1.055 Imidaclothiz Mixture 2T1.055 Thiacloprid Mixture 3 T1.055 Acetamiprid Mixture 4 T1.055Imidacloprid Mixture 5 T1.055 Nitenpyram Mixture 6 T1.055 DinotefuranMixture 7 T1.055 Clothianidin Mixture 1ii T1ii.055 Imidaclothiz Mixture2ii T1ii.055 Thiacloprid Mixture 3ii T1ii.055 Acetamiprid Mixture 4iiT1ii.055 Imidacloprid Mixture 5ii T1ii.055 Nitenpyram Mixture 6iiT1ii.055 Dinotefuran Mixture 7ii T1ii.055 Clothianidin Mixture 1iiiT1iii.055 Imidaclothiz Mixture 2iii T1iii.055 Thiacloprid Mixture 3iiiT1iii.055 Acetamiprid Mixture 4iii T1iii.055 Imidacloprid Mixture 5iiiT1iii.055 Nitenpyram Mixture 6iii T1iii.055 Dinotefuran Mixture 7iiiT1iii.055 Clothianidin

Preferably, the mixture is Mixture 3, more preferably at a weight ratioof the compound of formula I to acetamiprid of 1:8 to 8:1, even morepreferably at a weight ratio of 1:4 to 4:1.

Alternatively, the mixture is Mixture 3iii, more preferably at a weightratio of the compound of formula I to acetamiprid of 1:250 to 250:1,even more preferably at a weight ratio of 1:125 to 125:1, mostpreferably 1:50 to 50:1. In the most preferred embodiment, the weightratio is 16:1 to 1:16.

The present invention also relates to a method of controlling insects,acarines, nematodes or molluscs which comprises applying to a pest, to alocus of a pest, or to a plant susceptible to attack by a pest acombination of components A and B; seeds comprising a mixture ofcomponents A and B; and a method comprising coating a seed with amixture of components A and B.

Components A and B may be provided and/or used in amounts such that theyare capable of synergistic pest control. For example, the presentinvention includes pesticidal mixtures comprising a component A and acomponent B in a synergistically effective amount; agriculturalcompositions comprising a mixture of component A and B in asynergistically effective amount; the use of a mixture of component Aand B in a synergistically effective amount for combating animal pests;a method of combating animal pests which comprises contacting the animalpests, their habit, breeding ground, food supply, plant, seed, soil,area, material or environment in which the animal pests are growing ormay grow, or the materials, plants, seeds, soils, surfaces or spaces tobe protected from animal attack or infestation with a mixture ofcomponent A and B in a synergistically effective amount; a method forprotecting crops from attack or infestation by animal pests whichcomprises contacting a crop with a mixture of component A and B in asynergistically effective amount; a method for the protection of seedsfrom soil insects and of the seedlings' roots and shoots from soil andfoliar insects comprising contacting the seeds before sowing and/orafter pre-germination with a mixture of component A and B in asynergistically effective amount; seeds comprising, e.g. coated with, amixture of component A and B in a synergistically effective amount; amethod comprising coating a seed with a mixture of component A and B ina synergistically effective amount; a method of controlling insects,acarines, nematodes or molluscs which comprises applying to a pest, to alocus of a pest, or to a plant susceptible to attack by a pest acombination of components A and B in a synergistically effective amount.Mixtures of A and B will normally be applied in an insecticidally,acaricidally, nematicidally or molluscicidally effective amount. Inapplication components A and B may be applied simultaneously orseparately.

The mixtures of the present invention can be used to controlinfestations of insect pests such as Lepidoptera, Diptera, Hemiptera,Thysanoptera, Orthoptera, Dictyoptera, Coleoptera, Siphonaptera,Hymenoptera and Isoptera and also other invertebrate pests, for example,acarine, nematode and mollusc pests. Insects, acarines, nematodes andmolluscs are herein collectively referred to as pests. The pests whichmay be controlled by the use of the invention compounds include thosepests associated with agriculture (which term includes the growing ofcrops for food and fiber products), horticulture and animal husbandry,companion animals, forestry and the storage of products of vegetableorigin (such as fruit, grain and timber); those pests associated withthe damage of man-made structures and the transmission of diseases ofman and animals; and also nuisance pests (such as flies). The mixturesof the invention are particularly effective against insects, acarinesand/or nematodes. More particularly, the mixtures are effective againsthemipterans, acarines and nematodes.

According to the invention “useful plants” with which the mixtureaccording to the invention can be applied, typically comprise thefollowing species of plants: grape vines; cereals, such as wheat,barley, rye or oats; beet, such as sugar beet or fodder beet; fruits,such as pomes, stone fruits or soft fruits, for example apples, pears,plums, peaches, almonds, cherries, strawberries, raspberries orblackberries leguminous plants, such as beans, lentils, peas orsoybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers,coconut, castor oil plants, cocoa beans or groundnuts; cucumber plants,such as marrows, cucumbers or melons; fibre plants, such as cotton,flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit ormandarins; vegetables, such as spinach, lettuce, asparagus, cabbages,carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceae,such as avocados, cinnamon or camphor; maize; tobacco; nuts; coffee;sugar cane; tea; vines; hops; durian; bananas; natural rubber plants;turf or ornamentals, such as flowers, shrubs, broad-leaved trees orevergreens, for example conifers. This list does not represent anylimitation.

The term “useful plants” is to be understood as including also usefulplants that have been rendered tolerant to herbicides like bromoxynil orclasses of herbicides (such as, for example, HPPD inhibitors, ACCaseinhibitors, ALS inhibitors, for example primisulfuron, prosulfuron andtrifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase)inhibitors, GS (glutamine synthetase) inhibitors) as a result ofconventional methods of breeding or genetic engineering. An example of acrop that has been rendered tolerant to imidazolinones, e.g. imazamox,by conventional methods of breeding (mutagenesis) is Clearfield® summerrape (Canola). Examples of crops that have been rendered tolerant toherbicides or classes of herbicides by genetic engineering methodsinclude glyphosate- and glufosinate-resistant maize varietiescommercially available under the trade names RoundupReady®, Herculex I®and LibertyLink®.

The term “useful plants” is to be understood as including also usefulplants which have been so transformed by the use of recombinant DNAtechniques that they are capable of synthesising one or more selectivelyacting toxins, such as are known, for example, from toxin-producingbacteria, especially those of the genus Bacillus.

Toxins that can be expressed by such transgenic plants include, forexample, insecticidal proteins, for example insecticidal proteins fromBacillus cereus or Bacillus popilliae; or insecticidal proteins fromBacillus thuringiensis, such as δ-endotoxins, e.g. Cry1Ab, Cry1Ac,Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9c, or vegetativeinsecticidal proteins (Vip), e.g. Vip1, Vip2, Vip3 or Vip3A; orinsecticidal proteins of bacteria colonising nematodes, for examplePhotorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens,Xenorhabdus nematophilus; toxins produced by animals, such as scorpiontoxins, arachnid toxins, wasp toxins and other insect-specificneurotoxins; toxins produced by fungi, such as Streptomycetes toxins,plant lectins, such as pea lectins, barley lectins or snowdrop lectins;agglutinins; proteinase inhibitors, such as trypsine inhibitors, serineprotease inhibitors, patatin, cystatin, papain inhibitors;ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin,luffin, saporin or bryodin; steroid metabolism enzymes, such as3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase,cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ionchannel blockers, such as blockers of sodium or calcium channels,juvenile hormone esterase, diuretic hormone receptors, stilbenesynthase, bibenzyl synthase, chitinases and glucanases.

In the context of the present invention there are to be understood by6-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A,Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for exampleVip1, Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncatedtoxins and modified toxins. Hybrid toxins are produced recombinantly bya new combination of different domains of those proteins (see, forexample, WO 02/15701). An example for a truncated toxin is a truncatedCry1Ab, which is expressed in the Bt11 maize from Syngenta Seed SAS, asdescribed below. In the case of modified toxins, one or more amino acidsof the naturally occurring toxin are replaced. In such amino acidreplacements, preferably non-naturally present protease recognitionsequences are inserted into the toxin, such as, for example, in the caseof Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3Atoxin (see WO 03/018810)

Examples of such toxins or transgenic plants capable of synthesisingsuch toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278,WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.

The processes for the preparation of such transgenic plants aregenerally known to the person skilled in the art and are described, forexample, in the publications mentioned above. Cry1-type deoxyribonucleicacids and their preparation are known, for example, from WO 95/34656,EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

The toxin contained in the transgenic plants imparts to the plantstolerance to harmful insects. Such insects can occur in any taxonomicgroup of insects, but are especially commonly found in the beetles(Coleoptera), two-winged insects (Diptera) and butterflies(Lepidoptera).

Transgenic plants containing one or more genes that code for aninsecticidal resistance and express one or more toxins are known andsome of them are commercially available. Examples of such plants are:YieldGard® (maize variety that expresses a Cry1Ab toxin); YieldGardRootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGardPlus® (maize variety that expresses a Cry1Ab and a Cry3Bb1 toxin);Starlink® (maize variety that expresses a Cry9c toxin); Herculex I®(maize variety that expresses a Cry1 Fa2 toxin and the enzymephosphinothricine N-acetyltransferase (PAT) to achieve tolerance to theherbicide glufosinate ammonium); NuCOTN 33B® (cotton variety thatexpresses a Cry1Ac toxin); Bollgard I® (cotton variety that expresses aCry1Ac toxin); Bollgard II® (cotton variety that expresses a Cry1Ac anda Cry2Ab toxin); VipCOT® (cotton variety that expresses a Vip3A and aCry1Ab toxin); NewLeaf® (potato variety that expresses a Cry3A toxin);NatureGard® and Protecta®.

Further examples of such transgenic crops are:

1. Bt11 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a truncated Cry1Ab toxin. Bt11 maize alsotransgenically expresses the enzyme PAT to achieve tolerance to theherbicide glufosinate ammonium.

2. Bt176 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a Cry1Ab toxin. Bt176 maize also transgenicallyexpresses the enzyme PAT to achieve tolerance to the herbicideglufosinate ammonium.

3. MIR604 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Maize which hasbeen rendered insect-resistant by transgenic expression of a modifiedCry3A toxin. This toxin is Cry3A055 modified by insertion of acathepsin-G-protease recognition sequence. The preparation of suchtransgenic maize plants is described in WO 03/018810.

4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863expresses a Cry3Bb1 toxin and has resistance to certain Coleopterainsects.

5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/ES/96/02.

6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7B-1160 Brussels, Belgium, registration number C/NL/00/10. Geneticallymodified maize for the expression of the protein Cry1F for achievingresistance to certain Lepidoptera insects and of the PAT protein forachieving tolerance to the herbicide glufosinate ammonium.

7. NK603×MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue deTervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03.Consists of conventionally bred hybrid maize varieties by crossing thegenetically modified varieties NK603 and MON 810. NK603×MON 810 Maizetransgenically expresses the protein CP4 EPSPS, obtained fromAgrobacterium sp. strain CP4, which imparts tolerance to the herbicideRoundup® (contains glyphosate), and also a Cry1Ab toxin obtained fromBacillus thuringiensis subsp. kurstaki which brings about tolerance tocertain Lepidoptera, include the European corn borer.

Transgenic crops of insect-resistant plants are also described in BATS(Zentrum für Biosicherheit and Nachhaltigkeit, Zentrum BATS,Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http://bats.ch).

The term “useful plants” is to be understood as including also usefulplants which have been so transformed by the use of recombinant DNAtechniques that they are capable of synthesising antipathogenicsubstances having a selective action, such as, for example, theso-called “pathogenesis-related proteins” (PRPs, see e.g. EP-A-0 392225). Examples of such antipathogenic substances and transgenic plantscapable of synthesising such antipathogenic substances are known, forexample, from EP-A-0 392 225, WO 95/33818, and EP-A-0 353 191. Themethods of producing such transgenic plants are generally known to theperson skilled in the art and are described, for example, in thepublications mentioned above.

Antipathogenic substances which can be expressed by such transgenicplants include, for example, ion channel blockers, such as blockers forsodium and calcium channels, for example the viral KP1, KP4 or KP6toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases;the so-called “pathogenesis-related proteins” (PRPs; see e.g. EP-A-0 392225); antipathogenic substances produced by microorganisms, for examplepeptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818)or protein or polypeptide factors involved in plant pathogen defence(so-called “plant disease resistance genes”, as described in WO03/000906).

Useful plants of elevated interest in connection with present inventionare cereals; soybean; corn; cotton; rice; oil seed rape; sunflowers;sugarcane; pome fruits; stone fruits; citrus fruits; peanuts, potatoes;coffee; tea; strawberries; turf; vines and vegetables, such as tomatoes,cucurbits and lettuce.

The term “locus” of a useful plant as used herein is intended to embracethe place on which the useful plants are growing, where the plantpropagation materials of the useful plants are sown or where the plantpropagation materials of the useful plants will be placed into the soil.An example for such a locus is a field, on which crop plants aregrowing.

The term “plant propagation material” is understood to denote generativeparts of a plant, such as seeds, which can be used for themultiplication of the latter, and vegetative material, such as cuttingsor tubers, for example potatoes. There may be mentioned for exampleseeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes andparts of plants. Germinated plants and young plants which are to betransplanted after germination or after emergence from the soil, mayalso be mentioned. These young plants may be protected beforetransplantation by a total or partial treatment by immersion. Preferably“plant propagation material” is understood to denote seeds. Insecticidesthat are of particular interest for treating seeds include thiamethoxam,imidacloprid and clothianidin.

A further aspect of the instant invention is a method of protectingnatural substances of plant and/or animal origin, which have been takenfrom the natural life cycle, and/or their processed forms against attackof pests, which comprises applying to said natural substances of plantand/or animal origin or their processed forms a combination ofcomponents A and B in a synergistically effective amount.

According to the instant invention, the term “natural substances ofplant origin, which have been taken from the natural life cycle” denotesplants or parts thereof which have been harvested from the natural lifecycle and which are in the freshly harvested form. Examples of suchnatural substances of plant origin are stalks, leafs, tubers, seeds,fruits or grains. According to the instant invention, the term“processed form of a natural substance of plant origin” is understood todenote a form of a natural substance of plant origin that is the resultof a modification process. Such modification processes can be used totransform the natural substance of plant origin in a more storable formof such a substance (a storage good). Examples of such modificationprocesses are pre-drying, moistening, crushing, comminuting, grounding,compressing or roasting. Also falling under the definition of aprocessed form of a natural substance of plant origin is timber, whetherin the form of crude timber, such as construction timber, electricitypylons and barriers, or in the form of finished articles, such asfurniture or objects made from wood.

According to the instant invention, the term “natural substances ofanimal origin, which have been taken from the natural life cycle and/ortheir processed forms” is understood to denote material of animal originsuch as skin, hides, leather, furs, hairs and the like.

A preferred embodiment is a method of protecting natural substances ofplant origin, which have been taken from the natural life cycle, and/ortheir processed forms against attack of pests, which comprises applyingto said natural substances of plant and/or animal origin or theirprocessed forms a combination of components A and B in a synergisticallyeffective amount.

A further preferred embodiment is a method of protecting fruits,preferably pomes, stone fruits, soft fruits and citrus fruits, whichhave been taken from the natural life cycle, and/or their processedforms, which comprises applying to said fruits and/or their processedforms a combination of components A and B in a synergistically effectiveamount.

The combinations according to the present invention are furthermoreparticularly effective against the following pests: Myzus persicae(aphid), Aphis gossypii (aphid), Aphis fabae (aphid), Lygus spp.(capsids), Dysdercus spp. (capsids), Nilaparvata lugens (planthopper),Nephotettixc incticeps (leafhopper), Nezara spp. (stinkbugs), Euschistusspp. (stinkbugs), Leptocorisa spp. (stinkbugs), Frankliniellaoccidentalis (thrip), Thrips spp. (thrips), Leptinotarsa decemlineata(Colorado potato beetle), Anthonomus grandis (boll weevil), Aonidiellaspp. (scale insects), Trialeurodes spp. (white flies), Bemisia tabaci(white fly), Ostrinia nubilalis (European corn borer), Spodopteralittoralis (cotton leafworm), Heliothis virescens (tobacco budworm),Helicoverpa armigera (cotton bollworm), Helicoverpa zea (cottonbollworm), Sylepta derogata (cotton leaf roller), Pieris brassicae(white butterfly), Plutella xylostella (diamond back moth), Agrotis spp.(cutworms), Chilo suppressalis (rice stem borer), Locusta migratoria(locust), Chortiocetes terminifera (locust), Diabrotica spp.(rootworms), Panonychus ulmi (European red mite), Panonychus citri(citrus red mite), Tetranychus urticae (two-spotted spider mite),Tetranychus cinnabarinus (carmine spider mite), Phyllocoptruta oleivora(citrus rust mite), Polyphagotarsonemus latus (broad mite), Brevipalpusspp. (flat mites), Boophilus microplus (cattle tick), Dermacentorvariabilis (American dog tick), Ctenocephalides felis (cat flea),Liriomyza spp. (leafminer), Musca domestica (housefly), Aedes aegypti(mosquito), Anopheles spp. (mosquitoes), Culex spp. (mosquitoes),Lucillia spp. (blowflies), Blattella germanica (cockroach), Periplanetaamericana (cockroach), Blatta orientalis (cockroach), termites of theMastotermitidae (for example Mastotermes spp.), the Kalotermitidae (forexample Neotermes spp.), the Rhinotermitidae (for example Coptotermesformosanus, Reticulitermes flavipes, R. speratu, R. virginicus, R.hesperus, and R. santonensis) and the Termitidae (for exampleGlobitermes sulfureus), Solenopsis geminata (fire ant), Monomoriumpharaonis (pharaoh's ant), Damalinia spp. and Linognathus spp. (bitingand sucking lice), Meloidogyne spp. (root knot nematodes), Globoderaspp. and Heterodera spp. (cyst nematodes), Pratylenchus spp. (lesionnematodes), Rhodopholus spp. (banana burrowing nematodes), Tylenchulusspp. (citrus nematodes), Haemonchus contortus (barber pole worm),Caenorhabditis elegans (vinegar eelworm), Trichostrongylus spp. (gastrointestinal nematodes) and Deroceras reticulatum (slug), Diaphorina(psyllids), Cacopsylla, Paratrioza, and Brevipalpus (Leprosis mite).

In another embodiment, the combinations according to the presentinvention are also particularly effective against the following pests:

from the order Acarina, for example,

Acalitus spp, Aculus spp, Acaricalus spp, Aceria spp, Acarus siro,Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobiaspp, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae,Dermatophagoides spp, Eotetranychus spp, Eriophyes spp., Hemitarsonemusspp, Hyalomma spp., Ixodes spp., Olygonychus spp, Ornithodoros spp.,Polyphagotarsone latus, Panonychus spp., Phyllocoptruta oleivora,Phytonemus spp, Polyphagotarsonemus spp, Psoroptes spp., Rhipicephalusspp., Rhizoglyphus spp., Sarcoptes spp., Steneotarsonemus spp,Tarsonemus spp. and Tetranychus spp.;from the order Anoplura, for example,Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. andPhylloxera spp.;from the order Coleoptera, for example,Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp.,Aphodius spp, Astylus atromaculatus, Ataenius spp, Atomaria linearis,Chaetocnema tibialis, Cerotoma spp, Conoderus spp, Cosmopolites spp.,Cotinis nitida, Curculio spp., Cyclocephala spp, Dermestes spp.,Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp.,Heteronychus arator, Hypothenemus hampei, Lagria vilosa, LeptinotarsadecemLineata, Lissorhoptrus spp., Liogenys spp, Maecolaspis spp,Maladera castanea, Megascelis spp, Melighetes aeneus, Melolontha spp.,Myochrous armatus, Orycaephilus spp., Otiorhynchus spp., Phyllophagaspp, Phlyctinus spp., Popillia spp., Psylliodes spp., Rhyssomatusaubtilis, Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotrogaspp., Somaticus spp, Sphenophorus spp, Sternechus subsignatus, Tenebriospp., Tribolium spp. and Trogoderma spp.;from the order Diptera, for example,Aedes spp., Anopheles spp, Antherigona soccata, Bactrocea oleae, Bibiohortulanus, Bradysia spp, Calliphora erythrocephala, Ceratitis spp.,Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Delia spp,Drosophila melanogaster, Fannia spp., Gastrophilus spp., Geomyzatripunctata, Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyzaspp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp.,Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp.,Rhagoletis spp, Rivelia quadrifasciata, Scatella spp, Sciara spp.,Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.;from the order Hemiptera, for example,Acanthocoris scabrator, Acrosternum spp, Adelphocoris lineolatus,Amblypelta nitida, Bathycoelia thalassina, Blissus spp, Cimex spp.,Clavigralla tomentosicollis, Creontiades spp, Distantiella theobroma,Dichelops furcatus, Dysdercus spp., Edessa spp, Euchistus spp., Eurydemapulchrum, Eurygaster spp., Halyomorpha halys, Horcias nobilellus,Leptocorisa spp., Lygus spp, Margarodes spp, Murgantia histrionic,Neomegalotomus spp, Nesidiocoris tenuis, Nezara spp., Nysius simulans,Oebalus insularis, Piesma spp., Piezodorus spp, Rhodnius spp.,Sahlbergella singularis, Scaptocoris castanea, Scotinophara spp.,Thyanta spp, Triatoma spp., Vatiga illudens;Acyrthosium pisum, Adalges spp, Agalliana ensigera, Agonoscenatargionii, Aleurodicus spp, Aleurocanthus spp, Aleurolobus barodensis,Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula,Amritodus atkinsoni, Aonidiella spp., Aphididae, Aphis spp., Aspidiotusspp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp,Brachycaudus spp, Brevicoryne brassicae, Cacopsylla spp, Cavariellaaegopodii Scop., Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalusdictyospermi, Cicadella spp, Cofana spectra, Cryptomyzus spp, Cicadulinaspp, Coccus hesperidum, Dalbulus maidis, Dialeurodes spp, Diaphorinacitri, Diuraphis noxia, Dysaphis spp, Empoasca spp., Eriosoma larigerum,Erythroneura spp., Gascardia spp., Glycaspis brimblecombei, Hyadaphispseudobrassicae, Hyalopterus spp, Hyperomyzus pallidus, Idioscopusclypealis, Jacobiasca lybica, Laodelphax spp., Lecanium corni,Lepidosaphes spp., Lopaphis erysimi, Lyogenys maidis, Macrosiphum spp.,Mahanarva spp, Metcalfa pruinosa, Metopolophium dirhodum, Myndus crudus,Myzus spp., Neotoxoptera sp, Nephotettix spp., Nilaparvata spp.,Nippolachnus piri Mats, Odonaspis ruthae, Oregma lanigera Zehnter,Parabemisia myricae, Paratrioza cockerelli, Parlatoria spp., Pemphigusspp., Peregrinus maidis, Perkinsiella spp, Phorodon humuli, Phylloxeraspp, Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp.,Pseudatomoscelis seriatus, Psylla spp., Pulvinaria aethiopica,Quadraspidiotus spp., Quesada gigas, Recilia dorsalis, Rhopalosiphumspp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp.,Sogatella furcifera, Spissistilus festinus, Tarophagus Proserpina,Toxoptera spp, Trialeurodes spp, Tridiscus sporoboli, Trionymus spp,Trioza erytreae, Unaspis citri, Zygina flammigera, Zyginidiascutellaris;from the order Hymenoptera, for example,Acromyrmex, Arge spp, Atta spp., Cephus spp., Diprion spp., Diprionidae,Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis,Neodiprion spp., Pogonomyrmex spp, Slenopsis invicta, Solenopsis spp.and Vespa spp.;from the order Isoptera, for example,Coptotermes spp, Corniternes cumulans, Incisitermes spp, Macrotermesspp, Mastotermes spp, Microtermes spp, Reticulitermes spp.; Solenopsisgeminatefrom the order Lepidoptera, for example,Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabamaargillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp.,Argyresthia spp, Argyrotaenia spp., Autographa spp., Bucculatrixthurberiella, Busseola fusca, Cadra cautella, Carposina nipponensis,Chilo spp., Choristoneura spp., Chrysoteuchia topiaria, Clysiaambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp.,Coleophora spp., Colias lesbia, Cosmophila flava, Crambus spp,Crocidolomia binotalis, Cryptophlebia leucotreta, Cydalima perspectalis,Cydia spp., Diaphania perspectalis, Diatraea spp., Diparopsis castanea,Earias spp., Eldana saccharina, Ephestia spp., Epinotia spp, Estigmeneacrea, Etiella zinckinella, Eucosma spp., Eupoecilia ambiguella,Euproctis spp., Euxoa spp., Feltia jaculiferia, Grapholita spp., Hedyanubiferana, Heliothis spp., Hellula undalis, Herpetogramma spp,Hyphantria cunea, Keiferia lycopersicella, Lasmopalpus lignosellus,Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Loxostegebifidalis, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestrabrassicae, Manduca sexta, Mythimna spp, Noctua spp, Operophtera spp.,Orniodes indica, Ostrinia nubilalis, Pammene spp., Pandemis spp.,Panolis flammea, Papaipema nebris, Pectinophora gossypiela,Perileucoptera coffeella, Pseudaletia unipuncta, Phthorimaeaoperculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp.,Pseudoplusia spp, Rachiplusia nu, Richia albicosta, Scirpophaga spp.,Sesamia spp., Sparganothis spp., Spodoptera spp., Sylepta derogate,Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni, Tutaabsoluta, and Yponomeuta spp.;from the order Mallophaga, for example,Damalinea spp. and Trichodectes spp.;from the order Orthoptera, for example,Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae,Locusta spp., Neocurtilla hexadactyla, Periplaneta spp., Scapteriscusspp, and Schistocerca spp.;from the order Psocoptera, for example,Liposcelis spp.;from the order Siphonaptera, for example,Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis;from the order Thysanoptera, for example,Calliothrips phaseoli, Frankliniella spp., Heliothrips spp,Hercinothrips spp., Parthenothrips spp, Scirtothrips aurantii,Sericothrips variabilis, Taeniothrips spp., Thrips spp;from the order Thysanura, for example,Lepisma saccharina.

The active ingredients according to the invention can be used forcontrolling, i. e. containing or destroying, pests of the abovementionedtype which occur in particular on plants, especially on useful plantsand ornamentals in agriculture, in horticulture and in forests, or onorgans, such as fruits, flowers, foliage, stalks, tubers or roots, ofsuch plants, and in some cases even plant organs which are formed at alater point in time remain protected against these pests.

The mixtures of the invention may be used for pest control on variousplants, including soybean, alfalfa, brassicas (e.g. broccoli, cabbage,cauliflower), or oil crops, such as oilseed rape, mustard, canola,poppies, olives, sunflowers, coconut, castor, cocoa or ground nuts, orpotatoes (including sweet potatoes), almonds, fruiting vegetables (e.g.tomatoes, pepper, chili, eggplant, etc.), leafy vegetables (lettuce,spinach), bulb vegetables (e.g. onion, leek etc.), grapes, fruit, forinstance pomaceous fruit, stone fruit or soft fruit (e.g. apples, pears,plums, peaches, nectarines, almonds, cherries etc.) or berries, forexample strawberries, raspberries or blackberries.

Other suitable target crops are, in particular, cereals, such as wheat,barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodderbeet; leguminous crops, such as beans, lentils, peas, peanuts or soya;cucurbits, such as pumpkins, cucumbers, squash or melons; fibre plants,such as cotton, flax, hemp or jute; citrus fruit, such as oranges,lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce,asparagus, cabbages, carrots, onions, or bell peppers; Lauraceae, suchas avocado, Cinnamonium or camphor; and also tobacco, nuts (e.g. pecannuts, walnut), coffee, sugarcane, tea, pepper, grapevines, tropicalfruits (e.g. papaya, mango), hops, the plantain family, latex plants andornamentals. The mixtures of the invention can also be applied on turf,lawn and pastures.

The mixtures of the invention may be used on soybean to control, forexample, Elasmopalpus lignosellus, Diloboderus abderus, Diabroticaspeciosa, Sternechus subsignatus, Formicidae, Agrotis ipsilon, Julussspp., Anticarsia gemmatalis, Megascelis ssp., Procornitermes ssp.,Gryllotalpidae, Nezara viridula, Piezodorus spp., Acrosternum spp.,Neomegalotomus spp., Cerotoma trifurcata, Popillia japonica, Edessaspp., Liogenys fuscus, Euchistus heros, stalk borer, Scaptocoriscastanea, phyllophaga spp., Pseudoplusia includens, Spodoptera spp.,Bemisia tabaci, Agriotes spp. Aphis sp (e.g. Aphis glycines). Themixtures of the invention are preferably used on soybean to controlDiloboderus abderus, Diabrotica speciosa, Nezara viridula, Piezodorusspp., Acrosternum spp., Cerotoma trifurcata, Popillia japonica,Euchistus heros, phyllophaga spp., Agriotes sp, Aphis sp (e.g. Aphisglycines)

The mixtures of the invention may be used on corn to control, forexample, Euchistus heros, Dichelops furcatus, Diloboderus abderus,Elasmopalpus lignosellus, Spodoptera frugiperda, Nezara viridula,Cerotoma trifurcata, Popillia japonica, Agrotis ypsilon, Diabroticaspeciosa, Heteroptera, Procornitermes ssp., Scaptocoris castanea,Formicidae, Julus ssp., Dalbulus maidis, Diabrotica virgifera, Mocislatipes, Bemisia tabaci, heliothis spp., Tetranychus spp., thrips spp.,phyllophaga spp., scaptocoris spp., Liogenys fuscus, Spodoptera spp.,Ostrinia spp., Sesamia spp., Agriotes spp., Aphis sp. The mixtures ofthe invention are preferably used on corn to control Euchistus heros,Dichelops furcatus, Diloboderus abderus, Nezara viridula, Cerotomatrifurcata, Popillia japonica, Diabrotica speciosa, Diabroticavirgifera, Tetranychus spp., thrips spp., phyllophaga spp., scaptocorisspp., Agriotes spp., Aphis sp

The mixtures of the invention may be used on sugar cane to control, forexample, Sphenophorus spp., termites, Mahanarva spp. The mixtures of theinvention are preferably used on sugar cane to control termites,Mahanarva spp.

The mixtures of the invention may be used on alfalfa to control, forexample, Hypera brunneipennis, Hypera postica, Colias eurytheme, Collopsspp., Empoasca solana, Epitrix, Geocoris spp., Lygus hesperus, Lyguslineolaris, Spissistilus spp., Spodoptera spp., Trichoplusia ni. Themixtures of the invention are preferably used on alfalfa to controlHypera brunneipennis, Hypera postica, Empoasca solana, Epitrix, Lygushesperus, Lygus lineolaris, Trichoplusia ni.

The mixtures of the invention may be used on brassicas to control, forexample, Plutella xylostella, Pieris spp., Mamestra spp., Plusia spp.,Trichoplusia ni, Phyllotreta spp., Spodoptera spp., Empoasca solana,thrips spp., Spodoptera spp., Delia spp. Brevicoryne sp, Macrosiphum sp.The mixtures of the invention are preferably used on brassicas tocontrol Plutella xylostella Pieris spp., Plusia spp., Trichoplusia ni,Phyllotreta spp., thrips sp

The mixtures of the invention may be used on oil seed rape, e.g. canola,to control, for example, Meligethes spp., Ceutorhynchus napi, Psylloidesspp.

The mixtures of the invention may be used on potatoes, including sweetpotatoes, to control, for example, Empoasca spp., Leptinotarsa spp.,Diabrotica speciosa, Phthorimaea spp., Paratrioza spp., Maladeramatrida, Agriotes spp., Bemisia sp, Myzus sp., Macrosiphum sp. Aphis sp,Aulacorthum sp. Rhopalosiphum sp. The mixtures of the invention arepreferably used on potatoes, including sweet potatoes, to controlEmpoasca spp., Leptinotarsa spp., Diabrotica speciosa, Phthorimaea spp.,Paratrioza spp., Agriotes spp, Bemisia sp, Myzus sp., Macrosiphum sp.Aphis sp, Aulacorthum sp. Rhopalosiphum sp.

The mixtures of the invention may be used on cotton to control, forexample, Aphis gossypii, Anthonomus grandis, Pectinophora spp.,heliothis spp., Spodoptera spp., Tetranychus spp., Empoasca spp., thripsspp., Bemisia tabaci, Lygus spp., phyllophaga spp., Scaptocoris spp. Themixtures of the invention are preferably used on cotton to control Aphisgossypii, Anthonomus grandis, Tetranychus spp., Empoasca spp., thripsspp., Lygus spp., phyllophaga spp., Scaptocoris spp.

The mixtures of the invention may be used on rice to control, forexample, Nilaparvata lugens, Leptocorisa spp., Cnaphalocrosis spp.,Chilo spp., Scirpophaga spp., Lissorhoptrus spp., Oebalus pugnax. Themixtures of the invention are preferably used on rice to controlNilaparvata lugens, Leptocorisa spp., Lissorhoptrus spp., Oebaluspugnax.

The mixtures of the invention may be used on coffee to control, forexample, Brevipalpus sp, Hypothenemus Hampei, Perileucoptera Coffeella,Tetranychus spp. The mixtures of the invention are preferably used oncoffee to control Hypothenemus Hampel, Perileucoptera Coffeella,Brevipalpus sp. The mixtures of the invention may be used on citrus tocontrol, for example, Panonychus citri, Phyllocoptruta oleivora,Brevipalpus spp., Diaphorina citri, Scirtothrips spp., thrips spp.,Unaspis spp., Ceratitis capitata, Phyllocnistis spp., Brevipalpus sp.Aonidiella sp, Parlatoria sp, Ceroplastes sp, Planococcus sp,Pseudococcus sp., Tetranychus sp. Aphis sp. The mixtures of theinvention are preferably used on citrus to control Panonychus citri,Phyllocoptruta oleivora, Brevipalpus spp., Diaphorina citri,Scirtothrips spp., thrips spp., Phyllocnistis spp, Brevipalpus sp.Aonidiella sp, Parlatoria sp, Ceroplastes sp, Planococcus sp,Pseudococcus sp., Tetranychus sp., Aphis sp.

The mixtures of the invention may be used on almonds to control, forexample, Amyelois transitella, Tetranychus spp.

The mixtures of the invention may be used on fruiting vegetable,including tomatoes, pepper, chili, eggplant, cucumber, squash etc, tocontrol Myzus sp, Aphis sp, thrips spp., Tetranychus spp.,Polyphagotarsonemus spp., Aculops spp., Empoasca spp., Spodoptera spp.,heliothis spp., Tuta absoluta, Liriomyza spp., Bemisia tabaci,Trialeurodes spp., Paratrioza spp., Frankliniella occidentalis,Frankliniella spp., Anthonomus spp., Phyllotreta spp., Amrasca spp.,Epilachna spp., Halyomorpha spp., Scirtothrips spp., Leucinodes spp.,Neoleucinodes spp. The mixtures of the invention are preferably used onfruiting vegetable, including tomatoes, pepper, chili, eggplant,cucumber, squash etc, to control, for example, Myzus sp, Aphis sp,thrips spp., Tetranychus spp., Polyphagotarsonemus spp., Aculops spp.,Empoasca spp., Spodoptera spp., heliothis spp., Tuta absoluta, Liriomyzaspp., Paratrioza spp., Frankliniella occidentalis, Frankliniella spp.,Amrasca spp., Scirtothrips spp., Leucinodes spp., Neoleucinodes spp.

The mixtures of the invention may be used on tea to control, forexample, Pseudaulacaspis spp., Empoasca spp., Scirtothrips spp.,Caloptilia theivora. The mixtures of the invention are prefrerably usedon tea to control Empoasca spp., Scirtothrips spp.

The mixtures of the invention may be used on bulb vegetables, includingonion, leek etc to control, for example, thrips spp., Spodoptera spp.,heliothis spp. The mixtures of the invention are preferably used on bulbvegetables, including onion, leek etc to control thrips spp.

The mixtures of the invention may be used on grapes to control, forexample, Empoasca spp., Lobesia spp., Frankliniella spp., thrips spp.,Tetranychus spp., Rhipiphorothrips Cruentatus, EotetranychusWillamettei, Erythroneura Elegantula, Scaphoides spp, Pseudococcus sp,Planococcus sp The mixtures of the invention are preferably used ongrapes to control Frankliniella spp., thrips spp., Tetranychus spp.,Rhipiphorothrips Cruentatus, Scaphoides spp, Pseudococcus sp,Planococcus sp

The mixtures of the invention may be used on pome fruit, includingapples, pairs etc, to control, for example, Cacopsylla spp., Psyllaspp., Panonychus ulmi, Cydia pomonella, Quadraspidiotus sp, Lepidosaphessp, Aphis sp, Dysaphis sp, Eriosoma sp. The mixtures of the inventionare preferably used on pome fruit, including apples, pairs etc, tocontrol Cacopsylla spp., Psylla spp., Panonychus ulmi Quadraspidiotussp, Lepidosaphes sp, Aphis sp, Dysaphis sp, Eriosoma sp

The mixtures of the invention may be used on stone fruit to control, forexample, Grapholita molesta, Scirtothrips spp., thrips spp.,Frankliniella spp., Tetranychus spp., Myzus sp. The mixtures of theinvention are preferably used on stone fruit to control Scirtothripsspp., thrips spp., Frankliniella spp., Tetranychus spp., Myzus sp. Theamount of a combination of the invention to be applied, will depend onvarious factors, such as the compounds employed; the subject of thetreatment, such as, for example plants, soil or seeds; the type oftreatment, such as, for example spraying, dusting or seed dressing; thepurpose of the treatment, such as, for example prophylactic ortherapeutic; the type of pest to be controlled or the application time.

The invention also provides mixtures suitable for resistance management.In particular, the mixtures according to the invention are suitable forcontrolling insects, for example from the Hemiptera order such as aphids(e.g. Myzus spp), which are resistant to neonicotinoid insecticides. Themethod comprises applying to said neonicotinoid resistant insects amixture according to the invention.

The mixtures of the invention are particularly applicable to the controlof neonicotinoid resistant insects (and neonicotinoid resistance ininsects) of the order Hemiptera, such as: Acyrthosiphum pisum, Aphiscitricola, Aphis craccivora, Aphis fabae, Aphis frangulae, Aphisglycines, Aphis gossypii, Aphis nasturtii, Aphis pomi, Aphis spiraecola,Aulacorthum solani, Brachycaudus helichrysi, Brevicoryne brassicae,Diuraphis noxia, Dysaphis devecta, Dysaphis plantaginea, Eriosomalanigerum, Hyalopterus pruni, Lipaphis erysimi, Macrosiphum avenae,Macrosiphum euphorbiae, Macrosiphum rosae, Myzus cerasi F., Myzusnicotianae, Myzus persicae, Nasonovia ribisnigri, Pemphigus bursarius,Phorodon humuli, Rhopalosiphum insertum Wa, Rhopalosiphum maidis Fitch,Rhopalosiphum padi L., Schizaphis graminum Rond., Sitobion avenae,Toxoptera aurantii, Toxoptera citricola, Phylloxera vitifoliae,Acyrthosiphon dirhodum, Acyrthosiphon solani, Aphis forbesi, Aphisgrossulariae, Aphis idaei, Aphis illinoisensis, Aphis maidiradicis,Aphis ruborum, Aphis schneideri, Brachycaudus persicaecola, Cavariellaaegopodii Scop., Cryptomyzus galeopsidis, Cryptomyzus ribis, Hyadaphispseudobrassicae, Hyalopterus amygdali, Hyperomyzus pallidus,Macrosiphoniella sanborni, Metopolophium dirhodum, Myzus malisuctus,Myzus varians, Neotoxoptera sp, Nippolachnus piri Mats., Oregma lanigeraZehnter, Rhopalosiphum fitchii Sand., Rhopalosiphum nymphaeae,Rhopalosiphum sacchari Ze, Sappaphis piricola Okam.+T, Schizaphispiricola, Toxoptera theobromae Sch, and Phylloxera coccinea,

Aleurodicus dispersus, Aleurocanthus spiniferus, Aleurocanthus woglumi,Aleurodicus cocois, Aleurodicus destructor, Aleurolobus barodensis,Aleurothrixus floccosus, Bemisia tabaci, Bemisia argentifolli,Dialeurodes citri, Dialeurodes citrifolli, Parabemisia myricae,Trialeurodes packardi, Trialeurodes ricini, Trialeurodes vaporariorum,Trialeurodes variabilis,Agonoscena targionii, Bactericera cockerelli, Cacopsylla pyri,Cacopsylla pyricola, Cacopsylla pyrisuga, Diaphorina citri, Glycaspisbrimblecombei, Paratrioza cockerelli, Troza erytreae,Amarasca biguttula biguttula, Amritodus atkinsoni, Cicadella viridis,Cicadulina mbila, Cofana spectra, Dalbulus maidis, Empoasca decedens,Empoasca biguttula, Empoasca fabae, Empoasca vitis, Empoasca papaya,Idioscopus clypealis, Jacobiasca lybica, Laodelphax striatellus, Mynduscrudus, Nephotettix virescens, Nephotettix cincticeps, Nilaparvatalugens, Peregrinus maidis, Perkinsiella saccharicida, Perkinsiellavastatrix, Recilia dorsalis, Sogatella furcifera, Tarophagus Proserpina,Zygina flammigera,Acanthocoris scabrator, Adelphocoris lineolatus, Amblypelta nitida,Bathycoelia thalassina, Blissus leucopterus, Clavigrallatomentosicollis, Edessa meditabunda, Eurydema pulchrum, Eurydemarugosum, Eurygaster Maura, Euschistus servus, Euschistus tristigmus,Euschistus heros Helopeltis antonii, Horcias nobilellus, Leptocorisaacuta, Lygus lineolaris, Lygus hesperus, Murgantia histrionic,Nesidiocoris tenuis, Nezara viridula, Oebalus insularis, Scotinopharacoarctata,

Specific examples of neonicotinoid resistant Hemiptera include Bemisiatabaci, Myzus persicae, Nilaparvata lugens, Aphis gossypii, Trialeurodesvaporariorum, Bactericera cockerelli.

Preferably, the neonicotinoid resistant insects are one or more of as anexample Acyrthosiphum pisum, Aphis citricola, Aphis craccivora, Aphisfabae, Aphis frangulae, Aphis glycines, Aphis gossypii, Aphis nasturtii,Aphis pomi, Aphis spiraecola, Aulacorthum solani, Brachycaudushelichrysi, Brevicoryne brassicae, Diuraphis noxia, Dysaphis devecta,Dysaphis plantaginea, Eriosoma lanigerum, Hyalopterus pruni, Lipaphiserysimi, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphum rosae,Myzus cerasi F., Myzus nicotianae, Myzus persicae, Nasonovia ribisnigri,Pemphigus bursarius, Phorodon humuli, Rhopalosiphum insertum Wa,Rhopalosiphum maidis Fitch, Rhopalosiphum padi L., Schizaphis graminumRond., Sitobion avenae, Toxoptera aurantii, Toxoptera citricola,Phylloxera vitifoliae, Bemisia tabaci, Myzus persicae, Nilaparvatalugens, Aphis gossypii, Trialeurodes vaporariorum, Bactericeracockerelli.

More preferably, the neonicotinoid resistant insects are one or more ofas an example Bemisia tabaci, Myzus persicae, Nilaparvata lugens, Aphisgossypii, Trialeurodes vaporariorum, Bactericera cockerelli.

The mixtures comprising a compound of formula (I), e.g. those selectedfrom the tables above, and one or more active ingredients as describedabove can be applied, for example, in a single “ready-mix” form, in acombined spray mixture composed from separate formulations of the singleactive ingredient components, such as a “tank-mix”, and in a combineduse of the single active ingredients when applied in a sequentialmanner, i.e. one after the other with a reasonably short period, such asa few hours or days. The order of applying the compounds of formula (I)e.g. those selected from the tables above and the active ingredients asdescribed above is not essential for working the present invention.

The synergistic activity of the combination is apparent from the factthat the pesticidal activity of the composition of A+B is greater thanthe sum of the pesticidal activities of A and B.

The method of the invention comprises applying to the useful plants, thelocus thereof or propagation material thereof in admixture orseparately, a synergistically effective aggregate amount of a componentA and a component B.

Some of said combinations according to the invention have a systemicaction and can be used as foliar, soil and seed treatment pesticides.The invention also covers a a method comprising coating a seed with amixture of components A and B as defined above.

With the combinations according to the invention it is possible toinhibit or destroy the pests which occur in plants or in parts of plants(fruit, blossoms, leaves, stems, tubers, roots) in different usefulplants, while at the same time the parts of plants which grow later arealso protected from attack by pests.

The combinations of the present invention are of particular interest forcontrolling pests in various useful plants or their seeds, especially infield crops such as potatoes, tobacco and sugarbeets, and wheat, rye,barley, oats, rice, maize, lawns, cotton, soybeans, oil seed rape, pulsecrops, sunflower, coffee, sugarcane, fruit and ornamentals inhorticulture and viticulture, in vegetables such as cucumbers, beans andcucurbits.

The combinations according to the invention are applied by treating thepests, the useful plants, the locus thereof, the propagation materialthereof, the natural substances of plant and/or animal origin, whichhave been taken from the natural life cycle, and/or their processedforms, or the industrial materials threatened by pests, attack with acombination of components A and B in a synergistically effective amount.

The combinations according to the invention may be applied before orafter infection or contamination of the useful plants, the propagationmaterial thereof, the natural substances of plant and/or animal origin,which have been taken from the natural life cycle, and/or theirprocessed forms, or the industrial materials by the pests.

The combinations according to the invention can be used for controlling,i. e. containing or destroying, pests of the abovementioned type whichoccur on useful plants in agriculture, in horticulture and in forests,or on organs of useful plants, such as fruits, flowers, foliage, stalks,tubers or roots, and in some cases even on organs of useful plants whichare formed at a later point in time remain protected against thesepests.

When applied to the useful plants the compound of formula (I) isgenerally applied at a rate of 1 to 500 g a.i./ha in association with 1to 2000 g a.i./ha, of a compound of component B, depending on the classof chemical employed as component B.

Generally for plant propagation material, such as seed treatment,application rates can vary from 0.001 to 10 g/kg of seeds of activeingredients. When the combinations of the present invention are used fortreating seed, rates of 0.001 to 5 g of a compound of formula (I) per kgof seed, preferably from 0.01 to 1 g per kg of seed, and 0.001 to 5 g ofa compound of component B, per kg of seed, preferably from 0.01 to 1 gper kg of seed, are generally sufficient.

Spodoptera preferably means Spodoptera littoralis. Heliothis preferablymeans Heliothis virescens. Tetranychus preferably means Tetranychusurticae.

The compositions of the invention may be employed in any conventionalform, for example in the form of a twin pack, a powder for dry seedtreatment (DS), an emulsion for seed treatment (ES), a flowableconcentrate for seed treatment (FS), a solution for seed treatment (LS),a water dispersible powder for seed treatment (WS), a capsule suspensionfor seed treatment (CF), a gel for seed treatment (GF), an emulsionconcentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE),a capsule suspension (CS), a water dispersible granule (WG), anemulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion,oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oilmiscible flowable (OF), an oil miscible liquid (OL), a solubleconcentrate (SL), an ultra-low volume suspension (SU), an ultra-lowvolume liquid (UL), a technical concentrate (TK), a dispersibleconcentrate (DC), a wettable powder (WP), a soluble granule (SG) or anytechnically feasible formulation in combination with agriculturallyacceptable adjuvants.

Such compositions may be produced in conventional manner, e.g. by mixingthe active ingredients with appropriate formulation inerts (diluents,solvents, fillers and optionally other formulating ingredients such assurfactants, biocides, anti-freeze, stickers, thickeners and compoundsthat provide adjuvancy effects). Also conventional slow releaseformulations may be employed where long lasting efficacy is intended.Particularly formulations to be applied in spraying forms, such as waterdispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like),wettable powders and granules, may contain surfactants such as wettingand dispersing agents and other compounds that provide adjuvancyeffects, e.g. the condensation product of formaldehyde with naphthalenesulphonate, an alkylarylsulphonate, a lignin sulphonate, a fatty alkylsulphate, and ethoxylated alkylphenol and an ethoxylated fatty alcohol.

The compositions according to the invention can preferably additionallyinclude an additive comprising an oil of vegetable or animal origin, amineral oil, alkyl esters of such oils or mixtures of such oils and oilderivatives. The amount of oil additive used in the compositionaccording to the invention is generally from 0.01 to 10%, based on thespray mixture. For example, the oil additive can be added to the spraytank in the desired concentration after the spray mixture has beenprepared. Preferred oil additives comprise mineral oils or an oil ofvegetable origin, for example rapeseed oil such as ADIGOR® and MERO®,olive oil or sunflower oil, emulsified vegetable oil, such as AMIGO®(Rhône-Poulenc Canada Inc.), alkyl esters of oils of vegetable origin,for example the methyl derivatives, or an oil of animal origin, such asfish oil or beef tallow. A preferred additive contains, for example, asactive components essentially 80% by weight alkyl esters of fish oilsand 15% by weight methylated rapeseed oil, and also 5% by weight ofcustomary emulsifiers and pH modifiers. Especially preferred oiladditives comprise alkyl esters of C₈-C₂₂ fatty acids, especially themethyl derivatives of C₁₂-C₁₈ fatty acids, for example the methyl estersof lauric acid, palmitic acid and oleic acid, being important. Thoseesters are known as methyl laurate (CAS-111-82-0), methyl palmitate(CAS-112-39-0) and methyl oleate (CAS-112-62-9). A preferred fatty acidmethyl ester derivative is Emery® 2230 and 2231 (Cognis GmbH). Those andother oil derivatives are also known from the Compendium of HerbicideAdjuvants, 5th Edition, Southern Illinois University, 2000. Also,alkoxylated fatty acids can be used as additives in the inventivecompositions as well as polymethylsiloxane based additives, which havebeen described in WO08/037373.

The application and action of the oil additives can be further improvedby combining them with surface-active substances, such as non-ionic,anionic or cationic surfactants. Examples of suitable anionic, non-ionicand cationic surfactants are listed on pages 7 and 8 of WO 97/34485.Preferred surface-active substances are anionic surfactants of thedodecylbenzylsulfonate type, especially the calcium salts thereof, andalso non-ionic surfactants of the fatty alcohol ethoxylate type. Specialpreference is given to ethoxylated C₁₂-C₂₂ fatty alcohols having adegree of ethoxylation of from 5 to 40. Examples of commerciallyavailable surfactants are the Genapol types (Clariant AG). Alsopreferred are silicone surfactants, especially polyalkyl-oxide-modifiedheptamethyltrisiloxanes, which are commercially available e.g. as SilwetL-77®, and also perfluorinated surfactants. The concentration ofsurface-active substances in relation to the total additive is generallyfrom 1 to 30% by weight. Examples of oil additives that consist ofmixtures of oils or mineral oils or derivatives thereof with surfactantsare Edenor ME SU®, Turbocharge® (Syngenta AG, CH) and Actipron® (BP OilUK Limited, GB).

The said surface-active substances may also be used in the formulationsalone, that is to say without oil additives.

Furthermore, the addition of an organic solvent to the oiladditive/surfactant mixture can contribute to a further enhancement ofaction. Suitable solvents are, for example, Solvesso® (ESSO) andAromatic Solvent® (Exxon Corporation). The concentration of suchsolvents can be from 10 to 80% by weight of the total weight. Such oiladditives, which may be in admixture with solvents, are described, forexample, in U.S. Pat. No. 4,834,908. A commercially available oiladditive disclosed therein is known by the name MERGE® (BASFCorporation). A further oil additive that is preferred according to theinvention is SCORE® (Syngenta Crop Protection Canada.)

In addition to the oil additives listed above, in order to enhance theactivity of the compositions according to the invention it is alsopossible for formulations of alkylpyrrolidones, (e.g. Agrimax®) to beadded to the spray mixture. Formulations of synthetic latices, such as,for example, polyacrylamide, polyvinyl compounds or poly-1-p-menthene(e.g. Bond®, Courier® or Emerald®) can also be used. Solutions thatcontain propionic acid, for example Eurogkem Pen-e-trate®, can also bemixed into the spray mixture as activity-enhancing agents.

A seed dressing formulation is applied in a manner known per se to theseeds employing the combination of the invention and a diluent insuitable seed dressing formulation form, e.g. as an aqueous suspensionor in a dry powder form having good adherence to the seeds. Such seeddressing formulations are known in the art. Seed dressing formulationsmay contain the single active ingredients or the combination of activeingredients in encapsulated form, e.g. as slow release capsules ormicrocapsules. A typical a tank-mix formulation for seed treatmentapplication comprises 0.25 to 80%, especially 1 to 75%, of the desiredingredients, and 99.75 to 20%, especially 99 to 25%, of a solid orliquid auxiliaries (including, for example, a solvent such as water),where the auxiliaries can be a surfactant in an amount of 0 to 40%,especially 0.5 to 30%, based on the tank-mix formulation. A typicalpre-mix formulation for seed treatment application comprises 0.5 to99.9%, especially 1 to 95%, of the desired ingredients, and 99.5 to0.1%, especially 99 to 5%, of a solid or liquid adjuvant (including, forexample, a solvent such as water), where the auxiliaries can be asurfactant in an amount of 0 to 50%, especially 0.5 to 40%, based on thepre-mix formulation.

In general, the formulations include from 0.01 to 90% by weight ofactive agent, from 0 to 20% agriculturally acceptable surfactant and 10to 99.99% solid or liquid formulation inerts and adjuvant(s), the activeagent consisting of at least the compound of formula (I) together with acompound of component B, and optionally other active agents,particularly microbiocides or conservatives or the like. Concentratedforms of compositions generally contain in between about 2 and 80%,preferably between about 5 and 70% by weight of active agent.Application forms of formulation may for example contain from 0.01 to20% by weight, preferably from 0.01 to 5% by weight of active agent.Whereas commercial products will preferably be formulated asconcentrates, the end user will normally employ diluted formulations.

EXAMPLES

A synergistic effect exists whenever the action of an active ingredientcombination is greater than the sum of the actions of the individualcomponents.

The action to be expected E for a given active ingredient combinationobeys the so-called COLBY formula and can be calculated as follows(COLBY, S. R. “Calculating synergistic and antagonistic responses ofherbicide combination”. Weeds, Vol. 15, pages 20-22; 1967):

ppm=milligrams of active ingredient (=a.i.) per liter of spray mixture

X=% action by active ingredient A) using p ppm of active ingredient

Y=% action by active ingredient B) using q ppm of active ingredient.

According to COLBY, the expected (additive) action of active ingredientsA)+B) using p+q ppm of active ingredient is

$E = {X + Y - \frac{X \cdot Y}{100}}$

If the action actually observed (O) is greater than the expected action(E), then the action of the combination is super-additive, i.e. there isa synergistic effect. In mathematical terms the synergism factor SFcorresponds to O/E. In the agricultural practice an SF of ≧1.2 indicatessignificant improvement over the purely complementary addition ofactivities (expected activity), while an SF of ≦0.9 in the practicalapplication routine signals a loss of activity compared to the expectedactivity.

Table 45 shows mixtures of T1.055, T1 ii.055 and T1 iii.055 and aComponent B of the present invention to be used for demonstratingcontrol on a wide range of pests. As the percent of mortality cannotexceed 100 percent, the unexpected increase in insecticidal activity canbe greatest only when the separate active ingredient components aloneare at application rates providing considerably less than 100 percentcontrol. Synergy may not be evident at low application rates where theindividual active ingredient components alone have little activity.However, in some instances high activity can be observed forcombinations wherein individual active ingredient alone at the sameapplication rate have essentially no activity.

Myzus persicae (Green Peach Aphid):

feeding/residual contact activity, preventive

Sunflower leaf discs were placed on agar in a 24-well microtiter plateand sprayed with the DMSO test solutions of Mixtures (as provided byTable 45). After drying, the leaf discs were infested with an aphidpopulation of mixed ages. After an incubation period of 6 DAT (daysafter treatment), samples were checked for mortality. (1 PPM=1 mg l⁻¹)Results are shown in Table 46.

TABLE 46 AVERAGE DEAD IN % PPM AI AFTER 6 DAYS EXPECTED OBSERVEDT1iii.055 Acetamiprid T1iii.055 Acetamiprid MORTALITY MORTALITY 25 0.1 00 0 0 25 0.2 0 0 0 80  25 0.4 0 0 0 85* 25 0.8 0 0 0 85* 25 1.6 0 27 2770*Tetranychus urticae (Two-Spotted Spider Mite):feeding/contact activity, preventive

Bean leaf discs on agar in 24-well microtiter plates were sprayed withthe DMSO test solutions of certain Mixtures (as provided by Table 45).After drying, the leaf discs were infested with mite populations ofmixed ages. 8 days later, discs were checked for mortality againstmobile stages. (1 PPM=1 mg l⁻¹) Results are shown in Table 47 and 48.

TABLE 47 AVERAGE DEAD IN % PPM AI AFTER 8 DAYS EXPECTED OBSERVED T1.055Acetamiprid T1.055 Acetamiprid MORTALITY MORTALITY 200 50 50 0 50 65*200 100 50 0 50 85* 200 200 50 0 50 90* 200 400 50 0 50 85* 200 800 50 050 85*

TABLE 48 AVERAGE DEAD IN % PPM AI AFTER 8 DAYS EXPECTED OBSERVEDT1iii.055 Acetamiprid T1iii.055 Acetamiprid MORTALITY MORTALITY 12.5 5015 0 15 40* 12.5 100 15 0 15 65* 12.5 200 15 0 15 70* 12.5 400 15 0 1570* 12.5 800 15 0 15 70*

The invention claimed is:
 1. A pesticidal mixture comprising as activeingredient a mixture of component (A) and component (B), whereincomponent (A) is a compound of formula (I)

in which Q is i

X, Y and Z independently of each other are C₁₋₄alkyl, C₁₋₄haloalkyl,C₁₋₄ alkoxy, C₁₋₄ haloalkoxy or halogen; m and n, independently of eachother, are 0, 1, 2 or 3 and m+n is 0, 1, 2 or 3; G is hydrogen, a metal,an ammonium, a sulfonium or a latentiating group, wherein thelatentiating group is selected from —C(═O)—R^(a) and —C(═O)—O—R^(b),wherein R^(a) is selected from hydrogen, C₁-C₁₂alkyl, C₂-C₁₂alkenyl,C₂-C₁₂alkynyl, C₁-C₁₀haloalkyl and R^(b) is selected from C₁-C₁₂alkyl,C₂-C₁₂alkenyl, C₂-C₁₂alkynyl, and C₁-C₁₀haloalkyl; R is hydrogen,C₁₋₄alkyl, C₁₋₄haloalkyl; and A is C₁₋₄alkyl; or an agrochemicallyacceptable salt or an N-oxide thereof; component (B) is selected fromacetamiprid; wherein the weight ratio of component (A) to component (B)is from 500:1 to 1:100.
 2. A pesticidal mixture according to claim 1,wherein in the compound of formula (I) R is selected from the groupconsisting of hydrogen, methyl, ethyl, iso-propyl, n-propyl, tert-butyl,sec-butyl, iso-butyl, and n-butyl.
 3. A pesticidal mixture according toclaim 1, wherein in the compound of formula (I), X, Y and Z areselected, independently of each other, from the group consisting ofmethyl, ethyl, iso-propyl, n-propyl, methoxy, fluoro, bromo and chloro,when m+n is 1, 2 or
 3. 4. A pesticidal mixture according to claim 1,wherein in the compound of formula (I), A is methyl.
 5. A pesticidalmixture according to claim 1, wherein Q is (i), m is 1, n is 1, X ismethyl, Y is in the ortho position and is methyl, Z is in the paraposition and is chloro, G is —(C═O)—O—CH2CH3, A is methyl and R ismethyl.
 6. A pesticidal mixture according to claim 1, wherein themixture comprises an agricultural acceptable carrier and optionally asurfactant.
 7. A pesticidal mixture according to claim 1, wherein themixture comprises formulation adjuvants.
 8. A method of controllinginsects or acarines, which comprises applying to a pest, to a locus of apest, or to a plant susceptible to attack by a pest a combination ofcomponents (A) and (B), wherein the combination of components (A) and(B) is a mixture according to claim
 1. 9. The method according to claim8 wherein the components (A) and (B) slow down the spread of disease ina plant.
 10. The method according to claim 8 for controlling insects,wherein the insects are neonicotinoid resistant.
 11. A seed comprising amixture as defined in claim
 1. 12. A pesticidal mixture according toclaim 1, wherein the weight ratio of component (A) to component (B) isfrom 33:1 to 1:5.